Organosilica materials and uses thereof

ABSTRACT

Organosilica materials, which are a polymer of at least one independent monomer of Formula [Z 1 OZ 2 OSiCH 2 ] 3  (I), wherein Z 1  and Z 2  each independently represent a hydrogen atom, a C 1 -C 4  alkyl group or a bond to a silicon atom of another monomer and at least one other monomer is provided herein. Methods of preparing and processes of using the organosilica materials, e.g., for gas separation, color removal etc., are also provided herein.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/091,071 filed Dec. 12, 2014 and U.S. Provisional Application Ser.No. 62/091,077 filed Dec. 12, 2014, which are herein incorporated byreference in their entirety.

This application is also related to several other co-pending U.S.applications, filed on even date herewith and bearing Attorney DocketNos. 2014EM304-US2 (entitled “Organosilica Materials and Uses Thereof”),2014EM305-US2 (entitled “Methods of Producing Organosilica Materials andUses Thereof”), 2015EM382 (entitled “Aromatic Hydrogenation Catalystsand Uses Thereof”), 2015EM383 (entitled “Organosilica Materials and UsesThereof”), 2015EM385 (entitled “Organosilica Materials and UsesThereof”), 2015EM386 (entitled “Organosilica Materials and UsesThereof”), 2015EM387 (entitled “Coating Method Using OrganosilicaMaterials and Uses Thereof”), 2015EM388 (entitled “Membrane FabricationMethod Using Organosilica Materials and Uses Thereof”), 2015EM389(entitled “Adsorbent for Heteroatom Species Removal and Uses Thereof”),and 2015EM390 (entitled “Method for Separating Aromatic Compounds fromLube Basestocks”), the entire disclosures of each of which areincorporated by reference herein.

Additionally, this application is further related to several otherco-pending U.S. applications, filed on even date herewith and bearingAttorney Docket Nos. 2015EM375 (entitled “Organosilica Materials for Useas Adsorbents for Oxygenate Removal”), 2015EM376 (entitled “SupportedCatalyst for Olefin Polymerization”), 2015EM377 (entitled “SupportedCatalyst for Olefin Polymerization”), 2015EM378 (entitled “SupportedCatalyst for Olefin Polymerization”), and 2015EM379 (entitled “SupportedCatalyst for Olefin Polymerization”), the entire disclosures of each ofwhich are incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to organosilica materials, methods ofmaking and uses thereof.

BACKGROUND OF THE INVENTION

Porous inorganic solids have found great utility as catalysts andseparation media for industrial application. In particular, mesoporousmaterials, such as silicas and aluminas, having a periodic arrangementof mesopores are attractive materials for use in adsorption, separationand catalysis processes due to their uniform and tunable pores, highsurface areas and large pore volumes. The pore structure of suchmesoporous materials is large enough to absorb large molecules and thepore wall structure can be as thin as about 1 nm. Further, suchmesoporous materials are known to have large specific surface areas(e.g., 1000 m²/g) and large pore volumes (e.g., 1 cm³/g). For thesereasons, such mesoporous materials enable reactive catalysts, adsorbentscomposed of a functional organic compound, and other molecules torapidly diffuse into the pores and therefore, can be advantageous overzeolites, which have smaller pore sizes. Consequently, such mesoporousmaterials can be useful not only for catalysis of high-speed catalyticreactions, but also as large capacity adsorbents.

It was further discovered that the inclusion of some organic groups inthe mesoporous framework can provide adjustable reactive surfaces andalso contributes to uniformity in pore size, higher mechanical strength,and hydrothermal stability of the material. Thus, mesoporousorganosilica materials can exhibit unique properties compared tomesoporous silica such as enhanced hydrothermal stability, chemicalstability, and mechanical properties. Organic groups can be incorporatedusing bridged silsesquioxane precursors of the form Si—R—Si to formmesoporous organosilicas.

Mesoporous organosilicas are conventionally formed by the self-assemblyof the silsequioxane precursor in the presence of a structure directingagent, a porogen and/or a framework element. The precursor ishydrolysable and condenses around the structure directing agent. Thesematerials have been referred to as Periodic Mesoporous Organosilicates(PMOs), due to the presence of periodic arrays of parallel alignedmesoscale channels. For example, Landskron, K., et al. [Science,302:266-269 (2003)] report the self-assembly of1,3,5-tris[diethoxysila]cylcohexane [(EtO)₂SiCH₂]₃ in the presence of abase and the structure directing agent, cetyltrimethylammonium bromideto form PMOs that are bridged organosilicas with a periodic mesoporousframework, which consist of SiO₃R or SiO₂R₂ building blocks, where R isa bridging organic group. In PMOs, the organic groups can behomogenously distributed in the pore walls. U.S. Pat. Pub. No.2012/0059181 reports the preparation of a crystalline hybridorganic-inorganic silicate formed from 1,1,3,3,5,5 hexaethoxy-1,3,5trisilyl cyclohexane in the presence of NaAlO₂ and base. U.S. PatentApplication Publication No. 2007/003492 reports preparation of acomposition formed from 1,1,3,3,5,5 hexaethoxy-1,3,5 trisilylcyclohexane in the presence of propylene glycol monomethyl ether.

However, the use of a structure directing agent, such as a surfactant,in the preparation of an organosilica material, such as a PMO, requiresa complicated, energy intensive process to eliminate the structuredirecting agent at the end of the preparation process. This limits theability to scale-up the process for industrial applications. Therefore,there is a need to provide additional organosilica materials with adesirable pore diameter, pore volume and surface area. Further, there isa need to provide such organosilica materials that can be prepared by amethod that can be practiced in the absence of a structure directingagent, a porogen or surfactant.

SUMMARY OF THE INVENTION

It has been found that an organosilica material with desirable porediameter, pore volume, and surface area can be achieved. Further, suchorganosilica material can be successfully prepared without the need fora structure directing agent, a porogen or surfactant.

Thus, in one aspect, embodiments of the invention provide anorganosilica material, which is a polymer of at least one independentmonomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² eachindependently represent a hydrogen atom, a C₁-C₄ alkyl group or a bondto a silicon atom of another monomer and at least one other monomerselected from the group consisting of: (i) an independent unit ofFormula Z³OZ⁴Z⁵Z⁶ (II), wherein each Z³ represents a hydrogen atom, aC₁-C₄ alkyl group or a bond to a silicon atom of another monomer; andZ⁴, Z⁵ and Z⁶ are each independently selected from the group consistingof a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, anitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, a nitrogen-containing optionally substitutedheterocycloalkyl group, and an oxygen atom bonded to a silicon atom ofanother monomer; (ii) an independent unit of FormulaZ⁷Z⁸Z⁹Si—R¹—SiZ⁷Z⁸Z⁹ (III), wherein each Z⁷ independently represents ahydroxyl group, a C₁-C₄ alkoxy group or an oxygen bonded to a siliconatom of another comonomer; each Z⁸ and Z⁹ independently represent ahydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygenbonded to a silicon atom of another monomer; and R¹ represents anitrogen-containing C₂-C₁₀ alkylene group; and (iii) a combinationthereof.

In still another aspect, embodiments of the invention provide a gasseparation process comprising contacting a gas mixture containing atleast one contaminant with the organosilica material described herein.

In still another aspect, embodiments of the invention provide a processfor selectively separating a contaminant from a feed gas mixture, theprocess comprising: a) contacting the feed gas mixture under sorptionconditions with the organosilica material as described herein; b)adsorbing the contaminant into/onto the organosilica material; c)subjecting the organosilica material as described herein to desorptionconditions by which at least a portion of the sorbed contaminant isdesorbed; and d) retrieving a contaminant-rich product stream that has ahigher mol % of contaminant than the feed gas mixture.

Other embodiments, including particular aspects of the embodimentssummarized above, will be evident from the detailed description thatfollows.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an X-Ray Diffraction (XRD) spectrum for Sample 1A andComparative Sample 2.

FIG. 2a illustrates thermal gravimetric analysis (TGA) data for Sample1A in N₂.

FIG. 2b illustrates TGA data for Sample 1A in air.

FIG. 3 illustrates BET N₂ adsorption for Sample 1A, Comparative Sample 2and Sample 5.

FIG. 4 illustrates a BET pore diameter distribution for Sample 1A,Comparative Sample 2 and Sample 5.

FIG. 5 illustrates comparison of BET surface area and microporoussurface area for Sample 1A, Sample 3, Sample 5A and Sample 6.

FIG. 6 illustrates comparison of pore volume and pore diameter forSample 1A, Sample 3, Sample 5A and Sample 6.

FIG. 7a illustrates a ²⁹Si MAS NMR spectrum for Sample 1A.

FIG. 7b illustrates a ²⁹Si MAS NMR spectrum for Comparative Sample 2.

FIG. 8a illustrates TGA data for Comparative Sample 2 in N₂.

FIG. 8b illustrates TGA data for Comparative Sample 2 in air.

FIG. 9 illustrates an XRD spectrum for Sample 1A and Sample 3.

FIG. 10 illustrates a ²⁹Si MAS NMR spectrum for Sample 4A, Sample 4B,Sample 4C and Sample 4D.

FIG. 11 illustrates an XRD spectrum for Sample 5 and Sample 6.

FIG. 12 illustrates TGA data for Sample 5 in air and N₂.

FIG. 13 illustrates a ²⁹Si MAS NMR spectrum for Sample 1A and Sample 5.

FIG. 14 illustrates a ²⁹Si MAS NMR spectrum for Sample 7A and Sample 7B.

FIG. 15 illustrates an XRD spectrum for Sample 9, Sample 10, Sample 11A,and Sample 12.

FIG. 16 illustrates an XRD spectrum for Sample 13 and Sample 21.

FIG. 17 illustrates N₂ adsorption isotherms for Sample 13, Sample 14 andSample 15.

FIG. 18 illustrates pore diameter distribution for Sample 13, Sample 14and Sample 15.

FIG. 19 illustrates CO₂ adsorption isotherms at 40° C. for Sample 13A.

FIG. 20 illustrates CO₂ adsorption isotherms at 30° C. for Sample 17.

DETAILED DESCRIPTION OF THE INVENTION

In various aspects of the invention, organosilica materials, methods forpreparing organosilica materials and gas and liquid separation processesusing the organosilica materials are provided.

I. DEFINITIONS

For purposes of this invention and the claims hereto, the numberingscheme for the Periodic Table Groups is according to the IUPAC PeriodicTable of Elements.

The term “and/or” as used in a phrase such as “A and/or B” herein isintended to include “A and B”, “A or B”, “A”, and “B”.

The terms “substituent”, “radical”, “group”, and “moiety” may be usedinterchangeably.

As used herein, and unless otherwise specified, the term “C_(n)” meanshydrocarbon(s) having n carbon atom(s) per molecule, wherein n is apositive integer.

As used herein, and unless otherwise specified, the term “hydrocarbon”means a class of compounds containing hydrogen bound to carbon, andencompasses (i) saturated hydrocarbon compounds, (ii) unsaturatedhydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds(saturated and/or unsaturated), including mixtures of hydrocarboncompounds having different values of n.

As used herein, and unless otherwise specified, the term “alkyl” refersto a saturated hydrocarbon radical having from 1 to 12 carbon atoms(i.e. C₁-C₁₂ alkyl), particularly from 1 to 8 carbon atoms (i.e. C₁-C₈alkyl), particularly from 1 to 6 carbon atoms (i.e. C₁-C₆ alkyl), andparticularly from 1 to 4 carbon atoms (i.e. C₁-C₄ alkyl). Examples ofalkyl groups include, but are not limited to, methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, decyl, and so forth. The alkylgroup may be linear, branched or cyclic. “Alkyl” is intended to embraceall structural isomeric forms of an alkyl group. For example, as usedherein, propyl encompasses both n-propyl and isopropyl; butylencompasses n-butyl, sec-butyl, isobutyl and tert-butyl and so forth. Asused herein, “C₁ alkyl” refers to methyl (—CH₃), “C₂ alkyl” refers toethyl (—CH₂CH₃), “C₃ alkyl” refers to propyl (—CH₂CH₂CH₃) and “C₄ alkyl”refers to butyl (e.g. —CH₂CH₂CH₂CH₃, —(CH₃)CHCH₂CH₃, —CH₂CH(CH₃)₂,etc.). Further, as used herein, “Me” refers to methyl, and “Et” refersto ethyl, “i-Pr” refers to isopropyl, “t-Bu” refers to tert-butyl, and“Np” refers to neopentyl.

As used herein, and unless otherwise specified, the term “alkylene”refers to a divalent alkyl moiety containing 1 to 12 carbon atoms (i.e.C₁-C₁₂ alkylene) in length and meaning the alkylene moiety is attachedto the rest of the molecule at both ends of the alkyl unit. For example,alkylenes include, but are not limited to, —CH₂—, —CH₂CH₂—,—CH(CH₃)CH₂—, —CH₂CH₂CH₂—, etc. The alkylene group may be linear orbranched.

As used herein, and unless otherwise specified, the term“nitrogen-containing alkyl” refers to an alkyl group as defined hereinwherein one or more carbon atoms in the alkyl group is substituted witha nitrogen atom or a nitrogen-containing cyclic hydrocarbon having from2 to 10 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₁₀hydrocarbon), particularly having from 2 to 5 carbon atoms (i.e., anitrogen-containing cyclic C₂-C₅ hydrocarbon), and particularly havingfrom 2 to 5 carbon atoms (i.e., a nitrogen-containing cyclic C₂-C₅hydrocarbon). The nitrogen-containing cyclic hydrocarbon may have one ormore nitrogen atoms. The nitrogen atom(s) may optionally be substitutedwith one or two C₁-C₆ alkyl groups. The nitrogen-containing alkyl canhave from 1 to 12 carbon atoms (i.e. C₁-C₁₂ nitrogen-containing alkyl),particularly from 1 to 10 carbon atoms (i.e. C₁-C₁₀ nitrogen-containingalkyl), particularly from 2 to 10 carbon atoms (i.e. C₂-C₁₀nitrogen-containing alkyl), particularly from 3 to 10 carbon atoms (i.e.C₃-C₁₀ nitrogen-containing alkyl), and particularly from 3 to 8 carbonatoms (i.e. C₁-C₁₀ nitrogen-containing alkyl). Examples ofnitrogen-containing alkyls include, but are not limited to,

As used herein, and unless otherwise specified, the term“nitrogen-containing alkylene” refers to an alkylene group as definedherein wherein one or more carbon atoms in the alkyl group issubstituted with a nitrogen atom. The nitrogen atom(s) may optionally besubstituted with one or two C₁-C₆ alkyl groups. The nitrogen-containingalkylene can have from 1 to 12 carbon atoms (i.e. C₁-C₁₂nitrogen-containing alkylene), particularly from 2 to 10 carbon atoms(i.e. C₂-C₁₀ nitrogen-containing alkylene), particularly from 3 to 10carbon atoms (i.e. C₃-C₁₀ nitrogen-containing alkylene), particularlyfrom 4 to carbon atoms (i.e. C₄-C₁₀ nitrogen-containing alkylene), andparticularly from 3 to 8 carbon atoms (i.e. C₃-C₈ nitrogen-containingalkyl). Examples of nitrogen-containing alkylenes include, but are notlimited to,

As used herein, and unless otherwise specified, the term “alkenyl”refers to an unsaturated hydrocarbon radical having from 2 to 12 carbonatoms (i.e., C₂-C₁₂ alkenyl), particularly from 2 to 8 carbon atoms(i.e., C₂-C₈ alkenyl), particularly from 2 to 6 carbon atoms (i.e.,C₂-C₆ alkenyl), and having one or more (e.g., 2, 3, etc.) carbon-carbondouble bonds. The alkenyl group may be linear, branched or cyclic.Examples of alkenyls include, but are not limited to ethenyl (vinyl),2-propenyl, 3-propenyl, 1,4-pentadienyl, 1,4-butadienyl, 1-butenyl,2-butenyl and 3-butenyl. “Alkenyl” is intended to embrace all structuralisomeric forms of an alkenyl. For example, butenyl encompasses1,4-butadienyl, 1-butenyl, 2-butenyl and 3-butenyl, etc.

As used herein, and unless otherwise specified, the term “alkenylene”refers to a divalent alkenyl moiety containing 2 to about 12 carbonatoms (i.e. C₂-C₁₂ alkenylene) in length and meaning that the alkylenemoiety is attached to the rest of the molecule at both ends of the alkylunit. For example, alkenylenes include, but are not limited to, —CH═CH—,—CH═CHCH₂—, —CH═CH═CH—, —CH₂CH₂CH═CHCH₂—, etc. —CH₂CH₂—, —CH(CH₃)CH₂—,—CH₂CH₂CH₂—, etc. The alkenylene group may be linear or branched.

As used herein, and unless otherwise specified, the term “alkynyl”refers to an unsaturated hydrocarbon radical having from 2 to 12 carbonatoms (i.e., C₂-C₁₂ alkynyl), particularly from 2 to 8 carbon atoms(i.e., C₂-C₈ alkynyl), particularly from 2 to 6 carbon atoms (i.e.,C₂-C₆ alkynyl), and having one or more (e.g., 2, 3, etc.) carbon-carbontriple bonds. The alkynyl group may be linear, branched or cyclic.Examples of alkynyls include, but are not limited to ethynyl,1-propynyl, 2-butynyl, and 1,3-butadiynyl. “Alkynyl” is intended toembrace all structural isomeric forms of an alkynyl. For example,butynyl encompassses 2-butynyl, and 1,3-butadiynyl and propynylencompasses 1-propynyl and 2-propynyl (propargyl).

As used herein, and unless otherwise specified, the term “alkynylene”refers to a divalent alkynyl moiety containing 2 to about 12 carbonatoms (i.e. C₂-C₁₂ alkenylene) in length and meaning that the alkylenemoiety is attached to the rest of the molecule at both ends of the alkylunit. For example, alkenylenes include, but are not limited to, —C≡C—,—C≡CCH₂—, —C≡CCH₂C≡C—, —CH₂CH₂C≡CCH₂—, etc. —CH₂CH₂—, —CH(CH₃)CH₂—,—CH₂CH₂CH₂—, etc. The alkynlene group may be linear or branched.

As used herein, and unless otherwise specified, the term “alkoxy” refersto —O-alkyl containing from 1 to about 10 carbon atoms. The alkoxy maybe straight-chain or branched-chain. Non-limiting examples includemethoxy, ethoxy, propoxy, butoxy, isobutoxy, tert-butoxy, pentoxy, andhexoxy. “C₁ alkoxy” refers to methoxy, “C₂ alkoxy” refers to ethoxy, “C₃alkoxy” refers to propoxy and “C₄ alkoxy” refers to butoxy. Further, asused herein, “OMe” refers to methoxy and “OEt” refers to ethoxy.

As used herein, and unless otherwise specified, the term “aromatic”refers to unsaturated cyclic hydrocarbons having a delocalizedconjugated π system and having from 5 to 20 carbon atoms (aromaticC₅-C₂₀ hydrocarbon), particularly from 5 to 12 carbon atoms (aromaticC₅-C₁₂ hydrocarbon), and particularly from 5 to 10 carbon atoms(aromatic C₅-C₁₂ hydrocarbon). Exemplary aromatics include, but are notlimited to benzene, toluene, xylenes, mesitylene, ethylbenzenes, cumene,naphthalene, methylnaphthalene, dimethylnaphthalenes, ethylnaphthalenes,acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene,benzanthracenes, fluoranthrene, pyrene, chrysene, triphenylene, and thelike, and combinations thereof. Additionally, the aromatic may compriseone or more heteroatoms. Examples of heteroatoms include, but are notlimited to, nitrogen, oxygen, and/or sulfur. Aromatics with one or moreheteroatom include, but are not limited to furan, benzofuran, thiophene,benzothiophene, oxazole, thiazole and the like, and combinationsthereof. The aromatic may comprise monocyclic, bicyclic, tricyclic,and/or polycyclic rings (in some embodiments, at least monocyclic rings,only monocyclic and bicyclic rings, or only monocyclic rings) and may befused rings.

As used herein, and unless otherwise specified, the term “aryl” refersto any monocyclic or polycyclic cyclized carbon radical containing 6 to14 carbon ring atoms, wherein at least one ring is an aromatichydrocarbon. Examples of aryls include, but are not limited to phenyl,naphthyl, pyridinyl, and indolyl.

As used herein, and unless otherwise specified, the term “aralkyl”refers to an alkyl group substituted with an aryl group. The alkyl groupmay be a C₁-C₁₀ alkyl group, particularly a C₁-C₆, particularly a C₁-C₄alkyl group, and particularly a C₁-C₃ alkyl group. Examples of aralkylgroups include, but are not limited to phenymethyl, phenylethyl, andnaphthylmethyl. The aralkyl may comprise one or more heteroatoms and bereferred to as a “heteroaralkyl.” Examples of heteroatoms include, butare not limited to, nitrogen (i.e., nitrogen-containing heteroaralkyl),oxygen (i.e., oxygen-containing heteroaralkyl), and/or sulfur (i.e.,sulfur-containing heteroaralkyl). Examples of heteroaralkyl groupsinclude, but are not limited to, pyridinylethyl, indolylmethyl,furylethyl, and quinolinylpropyl.

As used herein, and unless otherwise specified, the term “heterocyclo”refers to fully saturated, partially saturated or unsaturated orpolycyclic cyclized carbon radical containing from 4 to 20 carbon ringatoms and containing one or more heteroatoms atoms. Examples ofheteroatoms include, but are not limited to, nitrogen (i.e.,nitrogen-containing heterocyclo), oxygen (i.e., oxygen-containingheterocyclo), and/or sulfur (i.e., sulfur-containing heterocyclo).Examples of heterocyclo groups include, but are not limited to, thienyl,furyl, pyrrolyl, piperazinyl, pyridyl, benzoxazolyl, quinolinyl,imidazolyl, pyrrolidinyl, and piperidinyl.

As used herein, and unless otherwise specified, the term“heterocycloalkyl” refers to an alkyl group substituted with heterocyclogroup. The alkyl group may be a C₁-C₁₀ alkyl group, particularly aC₁-C₆, particularly a C₁-C₄ alkyl group, and particularly a C₁-C₃ alkylgroup. Examples of heterocycloalkyl groups include, but are not limitedto thienylmethyl, furylethyl, pyrrolylmethyl, piperazinylethyl,pyridylmethyl, benzoxazolylethyl, quinolinylpropyl, andimidazolylpropyl.

As used herein, the term “hydroxyl” refers to an —OH group.

As used herein, the term “mesoporous” refers to solid materials havingpores that have a diameter within the range of from about 2 nm to about50 nm.

As used herein, the term “organosilica” refers to an organosiloxanecompound that comprises one or more organic groups bound to two or moreSi atoms.

As used herein, the term “silanol” refers to a Si—OH group.

As used herein, the term “silanol content” refers to the percent of theSi—OH groups in a compound and can be calculated by standard methods,such as NMR.

As used herein, the terms “structure directing agent,” “SDA,” and/or“porogen” refer to one or more compounds added to the synthesis media toaid in and/or guide the polymerization and/or polycondensing and/ororganization of the building blocks that form the organosilica materialframework. Further, a “porogen” is understood to be a compound capableof forming voids or pores in the resultant organosilica materialframework. As used herein, the term “structure directing agent”encompasses and is synonymous and interchangeable with the terms“templating agent” and “template.”

As used herein, and unless otherwise specified, the term “adsorption”includes physisorption, chemisorption, and condensation onto a solidmaterial and combinations thereof.

II. ORGANOSILICA MATERIALS

The invention relates to organosilica materials. In a first embodiment,the organosilica material may be a polymer of at least one independentmonomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² eachindependently can be a hydrogen atom, a C₁-C₄ alkyl group or a bond to asilicon atom of another siloxane and at least one other monomer selectedfrom the group consisting of:

-   -   (i) an independent unit of Formula Z³OZ⁴Z⁵Z⁶ (II), wherein each        Z³ represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to        a silicon atom of another monomer; and Z⁴, Z⁵ and Z⁶ are each        independently selected from the group consisting of a hydroxyl        group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a        nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing        heteroaralkyl group, a nitrogen-containing optionally        substituted heterocycloalkyl group, and an oxygen atom bonded to        a silicon atom of another monomer;    -   (ii) a unit of Formula Z⁷Z⁸Z⁹Si—R¹—SiZ⁷Z⁸Z⁹ (III), wherein each        Z⁷ independently represents a hydroxyl group, a C₁-C₄ alkoxy        group or an oxygen bonded to a silicon atom of another        comonomer; Each Z8 and Z9 independently represent a hydroxyl        group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygen        bonded to a silicon atom of another monomer; and each R¹        represents a nitrogen-containing C₂-C₁₀ alkylene group; and    -   (iii) a combination thereof.

As used herein, and unless otherwise specified, “a bond to a siliconatom of another monomer” means the bond can advantageously displace amoiety (particularly an oxygen-containing moiety such as a hydroxyl, analkoxy or the like), if present, on a silicon atom of the anothermonomer so there may be a bond directly to the silicon atom of theanother monomer thereby connecting the two monomers, e.g., via a Si—O—Silinkage. As used herein, and unless otherwise specified, “an oxygen atombonded to a silicon atom of another monomer” means that the oxygen atomcan advantageously displace a moiety (particularly an oxygen-containingmoiety such as a hydroxyl, an alkoxy or the like), if present, on asilicon atom of the another monomer so the oxygen atom may be bondeddirectly to the silicon atom of the another monomer thereby connectingthe two monomers, e.g., via a Si—O—Si linkage. For clarity, in theaforementioned bonding scenarios, the “another monomer” can be a monomerof the same type or a monomer of a different type.

II.A. Monomers of Formula (I)

In various embodiments, Z¹ and/or Z² each can be a hydrogen atom.

Additionally or alternatively, Z¹ and/or Z² each can be a C₁-C₄ alkylgroup, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, Z¹ and/or Z² each can be a bond to asilicon atom of another siloxane monomer.

Additionally or alternatively, Z¹ and Z² each independently can be ahydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom ofanother monomer.

Additionally or alternatively, Z¹ and Z² each independently can be ahydrogen atom, ethyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, Z¹ and Z² each independently can be ahydrogen atom or a bond to a silicon atom of another monomer.

II.B. Monomers of Formula (II)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I),such as another monomer having at least one independent unit of FormulaZ³OZ⁴Z⁵Z⁶Si (II), wherein each Z³ can be a hydrogen atom, a C₁-C₄ alkylgroup or a bond to a silicon atom of another monomer; and Z⁴, Z⁵ and Z⁶each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, anitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, and a nitrogen-containing optionally substitutedheterocycloalkyl group, and an oxygen atom bonded to a silicon atom ofanother monomer.

In various aspects, each Z³ can be a hydrogen atom.

Additionally or alternatively, each Z³ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z³ can be a hydrogen atom or a C₁-C₂alkyl group.

Additionally or alternatively, each Z³ can be a bond to a silicon atomof another monomer.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z³ can be a hydrogen atom, ethyl,methyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can be ahydroxyl group.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each independently can be a hydroxyl group.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can be ahydroxyl group or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each independently can be a hydroxyl group or a C₁-C₂ alkylgroup.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup and a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group and a C₁-C₂ alkoxy group.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can be anitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing C₁-C₉alkyl group, a nitrogen-containing C₁-C₈ alkyl group, anitrogen-containing C₁-C₇ alkyl group, a nitrogen-containing C₁-C₆ alkylgroup, a nitrogen-containing C₁-C₅ alkyl group, a nitrogen-containingC₁-C₄ alkyl group, a nitrogen-containing C₁-C₃ alkyl group, anitrogen-containing C₁-C₂ alkyl group, or a methylamine. In particular,Z⁴, Z⁵ and Z⁶ each independently can be a nitrogen-containing C₂-C₁₀alkyl group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₃-C₉ alkyl group, or a nitrogen-containing C₃-C₈alkyl group. The aforementioned nitrogen-containing alkyl groups mayhave one or more nitrogen atoms (e.g., 2, 3, etc.). Examples ofnitrogen-containing C₁-C₁₀ alkyl groups include, but are not limited to,

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group and a nitrogen-containing C₃-C₁₀ alkylgroup.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group and anitrogen-containing C₃-C₁₀ alkyl group.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can be anitrogen-containing heteroaralkyl group. The nitrogen-containingheteroaralkyl group can be a nitrogen-containing C₄-C₁₂ heteroaralkylgroup, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or anitrogen-containing C₄-C₈ heteroaralkyl group. Examples ofnitrogen-containing heteroaralkyl groups include but are not limited topyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl,pyrazinylethyl, and pyrazinylpropyl. The aforementionednitrogen-containing heteroaralkyl groups may have one or more nitrogenatoms (e.g., 2, 3, etc.).

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, nitrogen-containing C₃-C₁₀ alkyl group anda nitrogen-containing heteroaralkyl group.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group and a nitrogen-containingheteroaralkyl group.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can be anitrogen-containing heterocycloalkyl group, wherein the heterocycloalkylgroup may be optionally substituted with a C₁-C₆ alkyl group,particularly a C₁-C₄ alkyl group. The nitrogen-containingheterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀ heterocycloalkylgroup, or a nitrogen-containing C₄-C₈ heterocycloalkyl group. Examplesof nitrogen-containing heterocycloalkyl groups include but are notlimited to piperazinylethyl, piperazinylpropyl, piperidinylethyl,piperidinylpropyl. The aforementioned nitrogen-containingheterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3,etc.).

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can beselected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup, a C₁-C₂ alkoxy group, nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing heteroaralkyl group, and a nitrogen-containingoptionally substituted heterocycloalkyl group.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group and a nitrogen-containing optionally substitutedheterocycloalkyl group.

Additionally or alternatively, Z⁴, Z⁵ and Z⁶ each independently can bean oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, a nitrogen-containing optionally substitutedheterocycloalkyl group and an oxygen atom bonded to a silicon atom ofanother monomer.

Additionally or alternatively, each Z³ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵and Z⁶ each independently can be selected from the group consisting of ahydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, anitrogen-containing C₃-C₈ alkyl group, C₄-C₁₀ heteroaralkyl group, anitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkylgroup, and an oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z³ can be a hydrogen atom or a bondto a silicon atom of another monomer; and Z⁴, Z⁵ and Z⁶ eachindependently can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group, a nitrogen-containing C₃-C₈ alkyl group,C₄-C₁₀ heteroaralkyl group, a nitrogen-containing optionally substitutedC₄-C₁₀ heterocycloalkyl group, and an oxygen atom bonded to a siliconatom of another monomer.

In another particular embodiment, each Z³ can be a hydrogen atom, methylor a bond to a silicon atom of another comonomer; Z⁴ and Z⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, methoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁶ can be

In another particular embodiment, each Z³ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁴ and Z⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁶ can be

In another particular embodiment, each Z³ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁴ and Z⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁶ can be

In another particular embodiment, each Z³ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁴ and Z⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁶ can be

In another particular embodiment, each Z³ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁴ and Z⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁶ can be

In another particular embodiment, each Z³ can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z⁴ and Z⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and each Z⁶ can be

II.C. Monomers of Formula (III)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formula (II), such as another monomerhaving at least one independent unit of Formula Z⁷Z⁸Z⁹Si—R—SiZ⁷Z⁸Z⁹(III), wherein each Z⁷ independently can be a hydroxyl group, a C₁-C₄alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; Each Z8 and Z9 independently can a hydroxyl group, a C₁-C₄alkoxy group, a C₁-C₄ alkyl group or an oxygen atom bonded to a siliconatom of another monomer; and each R¹ can be a nitrogen-containing C₂-C₁₀alkylene group.

In various aspects, each Z⁷ can be a hydroxyl group.

Additionally or alternatively, each Z⁷ can be a C₁-C₄ alkoxy group, aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group or methoxy.

Additionally or alternatively, each Z⁷ can be a hydroxyl group or aC₁-C₂ alkoxy group.

Additionally or alternatively, each Z⁷ can be an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z⁷ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer.

Additionally or alternatively, each Z⁷ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z8 and Z9 independently can be ahydroxyl group.

Additionally or alternatively, each Z8 and Z9 independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, each Z8 and Z9 independently can be ahydroxyl group or a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z⁸ and Z⁹ independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z8 and Z9 independently can be ahydroxyl group, a C₁-C₂ alkoxy group, or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z8 and Z9 independently can be anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z8 and Z9 independently can be ahydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygenatom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z8 and Z9 independently can be ahydroxyl group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z⁷ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; and each Z8 and Z9 independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z⁷ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;and each Z8 and Z9 independently can be a hydroxyl group, ethoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁷ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; and each Z8and Z9 independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z⁷ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; and each Z8and Z9 independently can be a hydroxyl group or an oxygen atom bonded toa silicon atom of another comonomer.

Additionally or alternatively, each R¹ can be a nitrogen-containingC₂-C₁₀ alkylene group, a nitrogen-containing C₃-C₁₀ alkylene group, anitrogen-containing C₄-C₁₀ alkylene group, a nitrogen-containing C₄-C₉alkylene group, a nitrogen-containing C₄-C₈ alkylene group, or nitrogencontaining C₃-C₈ alkylene group. The aforementioned nitrogen-containingalkylene groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).Examples of nitrogen-containing alkylene groups include, but are notlimited to,

Additionally or alternatively, each Z⁷ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z8 and Z9 independently can be a hydroxyl group, a C₁-C₂alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to a siliconatom of another comonomer; and R¹ can be a nitrogen-containing C₄-C₁₀alkylene group.

Additionally or alternatively, each Z⁷ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z8 and Z9 independently can be a hydroxyl group, ethoxy, methoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer;and R can be selected from the group consisting of

Additionally or alternatively, each Z⁷ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; each Z8 andZ9 independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer; and R can be selectedfrom the group consisting of

Additionally or alternatively, each Z⁷ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; each Z⁸ andZ⁹ independently can be a hydroxyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R can be selected from the groupconsisting of

In another particular embodiment, each Z⁷ can be a hydroxyl group,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z⁸ and Z⁹ independently can be selected from the group consistingof a hydroxyl group, methoxy, and an oxygen atom bonded to a siliconatom of another monomer; and R can be

In another particular embodiment, each Z⁷ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;Z⁸ can be a hydroxyl group, ethoxy, and an oxygen atom bonded to asilicon atom of another monomer; Z¹⁹ can be methyl; and R can be

In another particular embodiment, each Z⁷ can be a hydroxyl group,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;Z⁸ can be a hydroxyl group, methoxy, and an oxygen atom bonded to asilicon atom of another monomer; Z⁹ can be methyl; and R can be

II.D. Monomers of Formula (IV)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formulas(II) and/or (III), such as anothermonomer having at least one independent unit of Formula [Z¹⁰OZ¹¹SiCH₂]₃(IV), wherein each Z¹ can be a hydrogen atom, a C₁-C₄ alkyl group or abond to a silicon atom of another monomer and each Z¹¹ can be a hydroxylgroup, a C₁-C₆ alkyl group or an oxygen atom bonded to a silicon atom ofanother monomer.

In various embodiments, each Z¹⁰ can be a hydrogen atom.

Additionally or alternatively, each Z¹⁰ can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z¹⁰ can be a hydrogen atom or aC₁-C₂ alkyl group.

Additionally or alternatively, each Z¹⁰ can be a bond to a silicon atomof another monomer.

Additionally or alternatively, each Z¹⁰ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z¹⁰ can be a hydrogen atom, ethyl ora bond to a silicon atom of another monomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group.

Additionally or alternatively, each Z¹¹ can be a C₁-C₆ alkyl group, aC₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group or methyl.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group or aC₁-C₄ alkyl group.

Additionally or alternatively, each Z¹¹ can be an oxygen atom bonded toa silicon atom of another monomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, a C₁-C₄alkyl group or an oxygen atom bonded to a silicon atom of anothermonomer.

Additionally or alternatively, each Z¹¹ can be a hydroxyl group, methylor an oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z¹⁰ can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer and Z¹¹ canbe a hydroxyl group, a C₁-C₄ alkyl group or an oxygen atom bonded to asilicon atom of another monomer.

Additionally or alternatively, each Z¹⁰ can be a hydrogen atom, ethyl ora bond to a silicon atom of another monomer and Z¹¹ can be a hydroxylgroup, methyl or an oxygen atom bonded to a silicon atom of anothermonomer.

Additionally or alternatively, each Z¹⁰ can be a hydrogen atom or a bondto a silicon atom of another monomer and each Z¹¹ can be a hydroxylgroup, methyl or an oxygen atom bonded to a silicon atom of anothermonomer.

II.E. Monomers of Formula (V)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formulas(II), (III) and/or (IV), such asanother monomer having at least one independent unit of FormulaZ¹²OZ¹³Z¹⁴Z¹⁵Si (V), wherein each Z¹² can be a hydrogen atom or a C₁-C₄alkyl group or a bond to a silicon atom of another monomer; and Z¹³, Z¹⁴and Z¹⁵ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group and anoxygen atom bonded to a silicon atom of another monomer.

In various aspects, each Z¹² can be a hydrogen atom.

Additionally or alternatively, each Z¹² can be a C₁-C₄ alkyl group, aC₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively, each Z¹² can be a hydrogen atom or aC₁-C₂ alkyl group.

Additionally or alternatively, each Z¹² can be a bond to a silicon atomof another monomer.

Additionally or alternatively, each Z¹² can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer.

Additionally or alternatively, each Z¹² can be a hydrogen atom, ethyl,methyl or a bond to a silicon atom of another monomer.

Additionally or alternatively, Z¹³, Z¹⁴ and Z¹⁵ each independently canbe a hydroxyl group.

Additionally or alternatively, each Z¹² can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z¹³, Z¹⁴and Z¹⁵ each independently can be a hydroxyl group.

Additionally or alternatively, Z¹³, Z¹⁴ and Z¹⁵ each independently canbe a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group ormethyl.

Additionally or alternatively, Z¹³, Z¹⁴ and Z¹⁵ each independently canbe a hydroxyl group or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z¹² can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z¹³, Z¹⁴and Z¹⁵ each independently can be a hydroxyl group or a C₁-C₂ alkylgroup.

Additionally or alternatively, Z¹³, Z¹⁴ and Z¹⁵ each independently canbe a C₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, Z¹³, Z¹⁴ and Z¹⁵ each independently canbe selected from the group consisting of a hydroxyl group, a C₁-C₂ alkylgroup and a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z¹² can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z¹³, Z¹⁴and Z¹⁵ each can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group and a C₁-C₂ alkoxy group.

Additionally or alternatively, Z¹³, Z¹⁴ and Z¹⁵ each independently canbe an oxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z¹² can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z¹³, Z¹⁴and Z¹⁵ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group, and anoxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z² can be a hydrogen atom, a C₁-C₂alkyl group or a bond to a silicon atom of another monomer; and Z¹³, Z¹⁴and Z¹⁵ each independently can be selected from the group consisting ofa hydroxyl group, a C₁-C₂ alkyl group, a C₁-C₂ alkoxy group and anoxygen atom bonded to a silicon atom of another monomer.

Additionally or alternatively, each Z¹² can be a hydrogen atom or a bondto a silicon atom of another monomer; and Z¹³, Z¹⁴ and Z¹⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, a C₁-C₂ alkyl group and an oxygen atom bonded to a silicon atomof another monomer.

In a particular embodiment, each Z¹² can be a hydrogen atom, ethyl or abond to a silicon atom of another monomer; and Z¹³, Z¹⁴ and Z¹⁵ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer.

In another particular embodiment, each Z¹² can be a hydrogen atom, ethylor a bond to a silicon atom of another comonomer; Z¹³ and Z¹⁴ eachindependently can be selected from the group consisting of a hydroxylgroup, ethoxy, and an oxygen atom bonded to a silicon atom of anothermonomer; and Z¹⁵ can be methyl.

II.E. Monomers of Formula (VI)

In various embodiments, the organosilica material may further compriseanother monomer in combination with independent units of Formula (I) andoptionally independent units Formulas(II), (III) (IV) and/or (V), suchas another monomer having at least one independent unit of FormulaZ¹⁶Z¹⁷Z¹⁸Si—R²—SiZ¹⁶Z¹⁷Z¹⁸ (VI), wherein each Z¹⁶ independentlyrepresents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen atombonded to a silicon atom of another comonomer; each Z¹⁷ and Z¹⁸independently represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄alkyl group or an oxygen atom bonded to a silicon atom of anothermonomer; and each R² is selected from the group consisting a C₁-C₈alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, anoptionally substituted C₆-C₂₀ aralkyl and an optionally substitutedC₄-C₂₀ heterocycloalkyl group.

In various aspects, each Z¹⁶ can be a hydroxyl group.

Additionally or alternatively, each Z¹⁶ can be a C₁-C₄ alkoxy group, aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group or methoxy.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group or aC₁-C₂ alkoxy group.

Additionally or alternatively, each Z¹⁶ can be an oxygen atom bonded toa silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁷ and Z¹⁸ independently can be ahydroxyl group.

Additionally or alternatively each Z¹⁷ and Z¹⁸ independently can be aC₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂ alkoxy group ormethoxy.

Additionally or alternatively, each Z¹⁷ and Z¹⁸ independently can be ahydroxyl group or a C₁-C₂ alkoxy group.

Additionally or alternatively, each Z¹⁷ and Z¹⁸ independently can be aC₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group or methyl.

Additionally or alternatively each Z¹⁷ and Z¹⁸ independently can be ahydroxyl group, a C₁-C₂ alkoxy group, or a C₁-C₂ alkyl group.

Additionally or alternatively, each Z¹⁷ and Z¹⁸ independently can be anoxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁷ and Z¹⁸ independently can be ahydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygenatom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁷ and Z¹⁸ independently can be ahydroxyl group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; and each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;and each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, ethoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; and each Z¹⁷and Z¹⁸ independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer.

Additionally or alternatively, each R² can be a C₁-C₈ alkylene group, aC₁-C₇ alkylene group, a C₁-C₆ alkylene group, a C₁-C₅ alkylene group, aC₁-C₄ alkylene group, a C₁-C₃ alkylene group, a C₁-C₂ alkylene group or—CH₂—.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be a C₁-C₄ alkylene group.

Additionally or alternatively, each R² can be a C₂-C₈ alkenylene group,a C₂-C₇ alkenylene group, a C₂-C₆ alkenylene group, a C₂-C₅ alkenylenegroup, a C₂-C₄ alkenylene group, a C₂-C₃ alkenylene group, or —HC═CH—.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be selected from the groupconsisting of a C₁-C₄ alkylene group and a C₂-C₄ alkenylene group.

Additionally or alternatively, each R² can be a C₂-C₈ alkynylene group,a C₂-C₇ alkynylene group, a C₂-C₆ alkynylene group, a C₂-C₅ alkynylenegroup, a C₂-C₄ alkynylene group, a C₂-C₃ alkynylene group, or —C≡C—.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be selected from the groupconsisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group and aC₂-C₄ alkynylene group.

Additionally or alternatively, each R² can be an optionally substitutedC₆-C₂₀ aralkyl, an optionally substituted C₆-C₁₄ aralkyl, or anoptionally substituted C₆-C₁₀ aralkyl. Examples of C₆-C₂₀ aralkylsinclude, but are not limited to, phenymethyl, phenylethyl, andnaphthylmethyl. The aralkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄ alkyl group.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be selected from the groupconsisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄alkynylene group, and an optionally substituted C₆-C₁₀ aralkyl.

Additionally or alternatively, each R² can be an optionally substitutedC₄-C₂₀ heterocycloalkyl group, an optionally substituted C₄-C₁₆heterocycloalkyl group, an optionally substituted C₄-C₁₂heterocycloalkyl group, or an optionally substituted C₄-C₁₀heterocycloalkyl group. Examples of C₄-C₂₀ heterocycloalkyl groupsinclude, but are not limited to, thienylmethyl, furylethyl,pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl,quinolinylpropyl, and imidazolylpropyl. The heterocycloalkyl may beoptionally substituted with a C₁-C₆ alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, a C₁-C₂alkoxy group or an oxygen atom bonded to a silicon atom of anothercomonomer; each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, aC₁-C₂ alkoxy group, a C₁-C₂ alkyl group, or an oxygen atom bonded to asilicon atom of another comonomer; and R² can be selected from the groupconsisting of a C₁-C₄ alkylene group, a C₂-C₄ alkenylene group, a C₂-C₄alkynylene group, an optionally substituted C₆-C₁₀ aralkyl and anoptionally substituted C₄-C₁₀ heterocycloalkyl group.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group, ethoxy,methoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹⁷ and Z¹⁸ independently can be a hydroxyl group, ethoxy, methoxy,methyl, or an oxygen atom bonded to a silicon atom of another comonomer;and R² can be selected from the group consisting of —CH₂—, —CH₂CH₂—, and—HC═CH—.

Additionally or alternatively, each Z¹⁶ can be a hydroxyl group or anoxygen atom bonded to a silicon atom of another comonomer; each Z¹⁷ andZ¹⁸ independently can be a hydroxyl group, methyl, or an oxygen atombonded to a silicon atom of another comonomer; and R² can be selectedfrom the group consisting of —CH₂—, —CH₂CH₂—, and —HC═CH—.

In a particular embodiment, each Z¹⁶ can be a hydroxyl group, ethoxy oran oxygen atom bonded to a silicon atom of another comonomer; each Z¹⁷can be a hydroxyl group, ethoxy, and an oxygen atom bonded to a siliconatom of another monomer; each Z¹⁸ can be methyl; and R² can be —CH₂CH₂—.

In another particular embodiment, each Z¹⁶ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹⁷ and Z¹⁸ independently can be selected from the group consistingof a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atomof another monomer; and R² can be —CH₂—.

In another particular embodiment, each Z¹⁶ can be a hydroxyl group,ethoxy or an oxygen atom bonded to a silicon atom of another comonomer;each Z¹⁷ and Z¹⁸ independently can be selected from the group consistingof a hydroxyl group, ethoxy, and an oxygen atom bonded to a silicon atomof another monomer; and R² can be —HC═CH—.

The organosilica materials made by the methods described herein can becharacterized as described in the following sections.

II.A. X-Ray Diffraction Peaks

The organosilica materials described herein can exhibit powder X-raydiffraction patterns with one broad peak between about 1 and about 4degrees 2θ, particularly one peak between about 1 and about 3 degrees2θ. In the 0.5 to 12 degrees 2θ range, the organosilica materials canexhibit substantially no peaks. The organosilica materials can exhibitsubstantially no peaks in the range of about 3 to about 12 degrees 2θ,about 4 to about 12 degrees 2θ, in the range of about 5 to about 12degrees 2θ, in the range of about 6 to about 12 degrees 2θ, in the rangeof about 7 to about 12 degrees 2θ, in the range of about 8 to about 12degrees 2θ, in the range of about 9 to about 12 degrees 2θ, in the rangeof about 10 to about 12 degrees 2θ, or in the range of about 11 to about12 degrees 2θ.

II.B. Silanol Content

The organosilica materials obtainable by the method of the invention canhave a silanol content that varies within wide limits, depending on thecomposition of the synthesis solution. The silanol content canconveniently be determined by solid state silicon NMR.

In various aspects, the organosilica material can have a silanol contentof greater than about 5%, greater than about 10%, greater than about15%, greater than about 20%, greater than about 25%, greater than about30%, greater than about 33%, greater than 35%, greater than about 40%,greater than about 41%, greater than about 44%, greater than about 45%,greater than about 50%, greater than about 55%, greater than about 60%,greater than about 65%, greater than about 70%, greater than about 75%,or about 80%. In certain embodiments, the silanol content can be greaterthan about 30% or greater than about 41%.

Additionally or alternatively, the organosilica material may have asilanol content of about 5% to about 80%, about 5% to about 75%, about5% to about 70%, about 5% to about 65%, about 5% to about 60%, about 5%to about 55%, about 5% to about 50%, about 5% to about 45%, about 5% toabout 44%, about 5% to about 41%, about 5% to about 40%, about 5% toabout 35%, about 5% to about 33%, about 5% to about 30%, about 5% toabout 25%, about 5% to about 20%, about 5% to about 15%, about 5% toabout 10%, about 10% to about 80%, about 10% to about 75%, about 10% toabout 70%, about 10% to about 65%, about 10% to about 60%, about 10% toabout 55%, about 10% to about 50%, about 10% to about 45%, about 10% toabout 44%, about 10% to about 41%, about 10% to about 40%, about 10% toabout 35%, about 10% to about 33%, about 10% to about 30%, about 10% toabout 25%, about 10% to about 20%, about 20% to about 80%, about 20% toabout 75%, about 20% to about 70%, about 20% to about 65%, about 20% toabout 60%, about 20% to about 55%, about 20% to about 50%, about 20% toabout 45%, about 20% to about 44%, about 20% to about 41%, about 20% toabout 40%, about 20% to about 35%, about 20% to about 33%, about 20% toabout 30%, about 20% to about 25%, about 30% to about 80%, about 30% toabout 75%, about 30% to about 70%, about 30% to about 65%, about 30% toabout 60%, about 30% to about 55%, about 30% to about 50%, about 30% toabout 45%, about 30% to about 44%, about 30% to about 41%, about 30% toabout 40%, about 30% to about 35%, about 30% to about 33%, about 40% toabout 80%, about 40% to about 75%, about 40% to about 70%, about 40% toabout 65%, about 40% to about 60%, about 40% to about 55%, about 40% toabout 50%, about 40% to about 45%, about 40% to about 44%, or about 40%to about 41%.

II.C. Pore Size

The organosilica material described herein are advantageously in amesoporous form. As indicated previously, the term mesoporous refers tosolid materials having pores with a diameter within the range of fromabout 2 nm to about 50 nm. The average pore diameter of the organosilicamaterial can be determined, for example, using nitrogenadsorption-desorption isotherm techniques within the expertise of one ofskill in the art, such as the BET (Brunauer Emmet Teller) method.

The organosilica material can have an average pore diameter of about 0.2nm, about 0.4 nm, about 0.5 nm, about 0.6 nm, about 0.8 nm, about 1.0nm, about 1.5 nm, about 1.8 nm or less than about 2.0 nm.

Additionally or alternatively, the organosilica material canadvantageously have an average pore diameter within the mesopore rangeof about 2.0 nm, about 2.5 nm, about 3.0 nm, about 3.1 nm, about 3.2 nm,about 3.3 nm, about 3.4 nm, about 3.5 nm, about 3.6 nm, about 3.7 nm,about 3.8 nm, about 3.9 nm about 4.0 nm, about 4.1 nm, about 4.5 nm,about 5.0 nm, about 6.0 nm, about 7.0 nm, about 7.3 nm, about 8 nm,about 8.4 nm, about 9 nm, about 10 nm, about 11 nm, about 13 nm, about15 nm, about 18 nm, about 20 nm, about 23 nm, about 25 nm, about 30 nm,about 40 nm, about 45 nm, or about 50 nm.

Additionally or alternatively, the organosilica material can have anaverage pore diameter of 0.2 nm to about 50 nm, about 0.2 nm to about 40nm, about 0.2 nm to about 30 nm, about 0.2 nm to about 25 nm, about 0.2nm to about 23 nm, about 0.2 nm to about 20 nm, about 0.2 nm to about 18nm, about 0.2 nm to about 15 nm, about 0.2 nm to about 13 nm, about 0.2nm to about 11 nm, about 0.2 nm to about 10 nm, about 0.2 nm to about 9nm, about 0.2 nm to about 8.4 nm, about 0.2 nm to about 8 nm, about 0.2nm to about 7.3 nm, about 0.2 nm to about 7.0 nm, about 0.2 nm to about6.0 nm, about 0.2 nm to about 5.0 nm, about 0.2 nm to about 4.5 nm,about 0.2 nm to about 4.1 nm, about 0.2 nm to about 4.0 nm, about 0.2 nmto about 3.9 nm, about 0.2 nm to about 3.8 nm, about 0.2 nm to about 3.7nm, about 0.2 nm to about 3.6 nm, about 0.2 nm to about 3.5 nm, about0.2 nm to about 3.4 nm, about 0.2 nm to about 3.3 nm, about 0.2 nm toabout 3.2 nm, about 0.2 nm to about 3.1 nm, about 0.2 nm to about 3.0nm, about 0.2 nm to about 2.5 nm, about 0.2 nm to about 2.0 nm, about0.2 nm to about 1.0 nm, about 1.0 nm to about 50 nm, about 1.0 nm toabout 40 nm, about 1.0 nm to about 30 nm, about 1.0 nm to about 25 nm,about 1.0 nm to about 23 nm, about 1.0 nm to about 20 nm, about 1.0 nmto about 18 nm, about 1.0 nm to about 15 nm, about 1.0 nm to about 13nm, about 1.0 nm to about 11 nm, about 1.0 nm to about 10 nm, about 1.0nm to about 9 nm, about 1.0 nm to about 8.4 nm, about 1.0 nm to about 8nm, about 1.0 nm to about 7.3 nm, about 1.0 nm to about 7.0 nm, about1.0 nm to about 6.0 nm, about 1.0 nm to about 5.0 nm, about 1.0 nm toabout 4.5 nm, about 1.0 nm to about 4.1 nm, about 1.0 nm to about 4.0nm, about 1.0 nm to about 3.9 nm, about 1.0 nm to about 3.8 nm, about1.0 nm to about 3.7 nm, about 1.0 nm to about 3.6 nm, about 1.0 nm toabout 3.5 nm, about 1.0 nm to about 3.4 nm, about 1.0 nm to about 3.3nm, about 1.0 nm to about 3.2 nm, about 1.0 nm to about 3.1 nm, about1.0 nm to about 3.0 nm or about 1.0 nm to about 2.5 nm.

In particular, the organosilica material can advantageously have anaverage pore diameter in the mesopore range of about 2.0 nm to about 50nm, about 2.0 nm to about 40 nm, about 2.0 nm to about 30 nm, about 2.0nm to about 25 nm, about 2.0 nm to about 23 nm, about 2.0 nm to about 20nm, about 2.0 nm to about 18 nm, about 2.0 nm to about 15 nm, about 2.0nm to about 13 nm, about 2.0 nm to about 11 nm, about 2.0 nm to about 10nm, about 2.0 nm to about 9 nm, about 2.0 nm to about 8.4 nm, about 2.0nm to about 8 nm, about 2.0 nm to about 7.3 nm, about 2.0 nm to about7.0 nm, about 2.0 nm to about 6.0 nm, about 2.0 nm to about 5.0 nm,about 2.0 nm to about 4.5 nm, about 2.0 nm to about 4.1 nm, about 2.0 nmto about 4.0 nm, about 2.0 nm to about 3.9 nm, about 2.0 nm to about 3.8nm, about 2.0 nm to about 3.7 nm, about 2.0 nm to about 3.6 nm, about2.0 nm to about 3.5 nm, about 2.0 nm to about 3.4 nm, about 2.0 nm toabout 3.3 nm, about 2.0 nm to about 3.2 nm, about 2.0 nm to about 3.1nm, about 2.0 nm to about 3.0 nm, about 2.0 nm to about 2.5 nm, about2.5 nm to about 50 nm, about 2.5 nm to about 40 nm, about 2.5 nm toabout 30 nm, about 2.5 nm to about 25 nm, about 2.5 nm to about 23 nm,about 2.5 nm to about 20 nm, about 2.5 nm to about 18 nm, about 2.5 nmto about 15 nm, about 2.5 nm to about 13 nm, about 2.5 nm to about 11nm, about 2.5 nm to about 10 nm, about 2.5 nm to about 9 nm, about 2.5nm to about 8.4 nm, about 2.5 nm to about 8 nm, about 2.5 nm to about7.3 nm, about 2.5 nm to about 7.0 nm, about 2.5 nm to about 6.0 nm,about 2.5 nm to about 5.0 nm, about 2.5 nm to about 4.5 nm, about 2.5 nmto about 4.1 nm, about 2.5 nm to about 4.0 nm, about 2.5 nm to about 3.9nm, about 2.5 nm to about 3.8 nm, about 2.5 nm to about 3.7 nm, about2.5 nm to about 3.6 nm, about 2.5 nm to about 3.5 nm, about 2.5 nm toabout 3.4 nm, about 2.5 nm to about 3.3 nm, about 2.5 nm to about 3.2nm, about 2.5 nm to about 3.1 nm, about 2.5 nm to about 3.0 nm, about3.0 nm to about 50 nm, about 3.0 nm to about 40 nm, about 3.0 nm toabout 30 nm, about 3.0 nm to about 25 nm, about 3.0 nm to about 23 nm,about 3.0 nm to about 20 nm, about 3.0 nm to about 18 nm, about 3.0 nmto about 15 nm, about 3.0 nm to about 13 nm, about 3.0 nm to about 11nm, about 3.0 nm to about 10 nm, about 3.0 nm to about 9 nm, about 3.0nm to about 8.4 nm, about 3.0 nm to about 8 nm, about 3.0 nm to about7.3 nm, about 3.0 nm to about 7.0 nm, about 3.0 nm to about 6.0 nm,about 3.0 nm to about 5.0 nm, about 3.0 nm to about 4.5 nm, about 3.0 nmto about 4.1 nm, or about 3.0 nm to about 4.0 nm.

In one particular embodiment, the organosilica material described hereincan have an average pore diameter of about 1.0 nm to about 30.0 nm,particularly about 1.0 nm to about 25.0 nm, particularly about 2.0 nm toabout 25.0 nm, particularly about 2.0 nm to about 20.0 nm, particularlyabout 2.0 nm to about 15.0 nm, particularly about 2.0 nm to about 10.0nm, or particularly about 3.0 nm to about 10.0 nm.

Using surfactant as a template to synthesize mesoporous materials cancreate highly ordered structure, e.g. well-defined cylindrical-like porechannels. In some circumstances, there may be no hysteresis loopobserved from N₂ adsorption isotherm. In other circumstances, forinstance where mesoporous materials can have less ordered porestructures, a hysteresis loop may be observed from N2 adsorptionisotherm experiments. In such circumstances, without being bound bytheory, the hysteresis can result from the lack of regularity in thepore shapes/sizes and/or from bottleneck constrictions in such irregularpores.

II.D. Surface Area

The surface area of the organosilica material can be determined, forexample, using nitrogen adsorption-desorption isotherm techniques withinthe expertise of one of skill in the art, such as the BET (BrunauerEmmet Teller) method. This method may determine a total surface area, anexternal surface area, and a microporous surface area. As used herein,and unless otherwise specified, “total surface area” refers to the totalsurface area as determined by the BET method. As used herein, and unlessotherwise specified, “microporous surface area” refers to microporoussurface are as determined by the BET method.

In various embodiments, the organosilica material can have a totalsurface area greater than or equal to about 100 m²/g, greater than orequal to about 200 m²/g, greater than or equal to about 300 m²/g,greater than or equal to about 400 m²/g, greater than or equal to about450 m²/g, greater than or equal to about 500 m²/g, greater than or equalto about 550 m²/g, greater than or equal to about 600 m²/g, greater thanor equal to about 700 m²/g, greater than or equal to about 800 m²/g,greater than or equal to about 850 m²/g, greater than or equal to about900 m²/g, greater than or equal to about 1,000 m²/g, greater than orequal to about 1,050 m²/g, greater than or equal to about 1,100 m²/g,greater than or equal to about 1,150 m²/g, greater than or equal toabout 1,200 m²/g, greater than or equal to about 1,250 m²/g, greaterthan or equal to about 1,300 m²/g, greater than or equal to about 1,400m²/g, greater than or equal to about 1,450 m²/g, greater than or equalto about 1,500 m²/g, greater than or equal to about 1,550 m²/g, greaterthan or equal to about 1,600 m²/g, greater than or equal to about 1,700m²/g, greater than or equal to about 1,800 m²/g, greater than or equalto about 1,900 m²/g, greater than or equal to about 2,000 m²/g, greaterthan or equal to greater than or equal to about 2,100 m²/g, greater thanor equal to about 2,200 m²/g, greater than or equal to about 2,300 m²/gor about 2,500 m²/g.

Additionally or alternatively, the organosilica material may have atotal surface area of about 50 m²/g to about 2,500 m²/g, about 50 m²/gto about 2,000 m²/g, about 50 m²/g to about 1,500 m²/g, about 50 m²/g toabout 1,000 m²/g, about 100 m²/g to about 2,500 m²/g, about 100 m²/g toabout 2,300 m²/g, about 100 m²/g to about 2,200 m²/g, about 100 m²/g toabout 2,100 m²/g, about 100 m²/g to about 2,000 m²/g, about 100 m²/g toabout 1,900 m²/g, about 100 m²/g to about 1,800 m²/g, about 100 m²/g toabout 1,700 m²/g, about 100 m²/g to about 1,600 m²/g, about 100 m²/g toabout 1,550 m²/g, about 100 m²/g to about 1,500 m²/g, about 100 m²/g toabout 1,450 m²/g, about 100 m²/g to about 1,400 m²/g, about 100 m²/g toabout 1,300 m²/g, about 100 m²/g to about 1,250 m²/g, about 100 m²/g toabout 1,200 m²/g, about 100 m²/g to about 1,150 m²/g, about 100 m²/g toabout 1,100 m²/g, about 100 m²/g to about 1,050 m²/g, about 100 m²/g toabout 1,000 m²/g, about 100 m²/g to about 900 m²/g, about 100 m²/g toabout 850 m²/g, about 100 m²/g to about 800 m²/g, about 100 m²/g toabout 700 m²/g, about 100 m²/g to about 600 m²/g, about 100 m²/g toabout 550 m²/g, about 100 m²/g to about 500 m²/g, about 100 m²/g toabout 450 m²/g, about 100 m²/g to about 400 m²/g, about 100 m²/g toabout 300 m²/g, about 100 m²/g to about 200 m²/g, about 200 m²/g toabout 2,500 m²/g, about 200 m²/g to about 2,300 m²/g, about 200 m²/g toabout 2,200 m²/g, about 200 m²/g to about 2,100 m²/g, about 200 m²/g toabout 2,000 m²/g, about 200 m²/g to about 1,900 m²/g, about 200 m²/g toabout 1,800 m²/g, about 200 m²/g to about 1,700 m²/g, about 200 m²/g toabout 1,600 m²/g, about 200 m²/g to about 1,550 m²/g, about 200 m²/g toabout 1,500 m²/g, about 200 m²/g to about 1,450 m²/g, about 200 m²/g toabout 1,400 m²/g, about 200 m²/g to about 1,300 m²/g, about 200 m²/g toabout 1,250 m²/g, about 200 m²/g to about 1,200 m²/g, about 200 m²/g toabout 1,150 m²/g, about 200 m²/g to about 1,100 m²/g, about 200 m²/g toabout 1,050 m²/g, about 200 m²/g to about 1,000 m²/g, about 200 m²/g toabout 900 m²/g, about 200 m²/g to about 850 m²/g, about 200 m²/g toabout 800 m²/g, about 200 m²/g to about 700 m²/g, about 200 m²/g toabout 600 m²/g, about 200 m²/g to about 550 m²/g, about 200 m²/g toabout 500 m²/g, about 200 m²/g to about 450 m²/g, about 200 m²/g toabout 400 m²/g, about 200 m²/g to about 300 m²/g, about 500 m²/g toabout 2,500 m²/g, about 500 m²/g to about 2,300 m²/g, about 500 m²/g toabout 2,200 m²/g, about 500 m²/g to about 2,100 m²/g, about 500 m²/g toabout 2,000 m²/g, about 500 m²/g to about 1,900 m²/g, about 500 m²/g toabout 1,800 m²/g, about 500 m²/g to about 1,700 m²/g, about 500 m²/g toabout 1,600 m²/g, about 500 m²/g to about 1,550 m²/g, about 500 m²/g toabout 1,500 m²/g, about 500 m²/g to about 1,450 m²/g, about 500 m²/g toabout 1,400 m²/g, about 500 m²/g to about, 300 m²/g, about 500 m²/g toabout 1,250 m²/g, about 500 m²/g to about 1,200 m²/g, about 500 m²/g toabout 1,150 m²/g, about 500 m²/g to about 1,100 m²/g, about 500 m²/g toabout 1,050 m²/g, about 500 m²/g to about 1,000 m²/g, about 500 m²/g toabout 900 m²/g, about 500 m²/g to about 850 m²/g, about 500 m²/g toabout 800 m²/g, about 500 m²/g to about 700 m²/g, about 500 m²/g toabout 600 m²/g, about 500 m²/g to about 550 m²/g, about 1,000 m²/g toabout 2,500 m²/g, about 1,000 m²/g to about 2,300 m²/g, about 1,000 m²/gto about 2,200 m²/g, about 1,000 m²/g to about 2,100 m²/g, about 1,000m²/g to about 2,000 m²/g, about 1,000 m²/g to about 1,900 m²/g, about1,000 m²/g to about 1,800 m²/g, about 1,000 m²/g to about 1,700 m²/g,about 1,000 m²/g to about 1,600 m²/g, about 1,000 m²/g to about 1,550m²/g, about 1,000 m²/g to about 1,500 m²/g, about 1,000 m²/g to about1,450 m²/g, about 1,000 m²/g to about 1,400 m²/g, about 1,000 m²/g toabout 1,300 m²/g, about 1,000 m²/g to about 1,250 m²/g, about 1,000 m²/gto about 1,200 m²/g, about 1,000 m²/g to about 1,150 m²/g, about 1,000m²/g to about 1,100 m²/g, or about 1,000 m²/g to about 1,050 m²/g.

In one particular embodiment, the organosilica material described hereinmay have a total surface area of about 200 m²/g to about 2,500 m²g,particularly about 400 m²/g to about 2,500 m²g, particularly about 400m²/g to about 2,000 m²/g, particularly about 500 m²/g to about 2,000m²/g, or particularly about 400 m²/g to about 1,500 m²/g.

III.E. Pore Volume

The pore volume of the organosilica material made by the methodsdescribed herein can be determined, for example, using nitrogenadsorption-desorption isotherm techniques within the expertise of one ofskill in the art, such as the BET (Brunauer Emmet Teller) method.

In various embodiments, the organosilica material can have a pore volumegreater than or equal to about 0.1 cm³/g, greater than or equal to about0.2 cm³/g, greater than or equal to about 0.3 cm³/g, greater than orequal to about 0.4 cm³/g, greater than or equal to about 0.5 cm³/g,greater than or equal to about 0.6 cm³/g, greater than or equal to about0.7 cm³/g, greater than or equal to about 0.8 cm³/g, greater than orequal to about 0.9 cm³/g, greater than or equal to about 1.0 cm³/g,greater than or equal to about 1.1 cm³/g, greater than or equal to about1.2 cm³/g, greater than or equal to about 1.3 cm³/g, greater than orequal to about 1.4 cm³/g, greater than or equal to about 1.5 cm³/g,greater than or equal to about 1.6 cm³/g, greater than or equal to about1.7 cm³/g, greater than or equal to about 1.8 cm³/g, greater than orequal to about 1.9 cm³/g, greater than or equal to about 2.0 cm³/g,greater than or equal to about 2.5 cm³/g, greater than or equal to about3.0 cm³/g, greater than or equal to about 3.5 cm³/g, greater than orequal to about 4.0 cm³/g, greater than or equal to about 5.0 cm³/g,greater than or equal to about 6.0 cm³/g, greater than or equal to about7.0 cm³/g, or about 10.0 cm³/g.

Additionally or alternatively, the organosilica material can have a porevolume of about 0.1 cm³/g to about 10.0 cm³/g, about 0.1 cm³/g to about7.0 cm³/g, about 0.1 cm³/g to about 6.0 cm³/g, about 0.1 cm³/g to about5.0 cm³/g, about 0.1 cm³/g to about 4.0 cm³/g, about 0.1 cm³/g to about3.5 cm³/g, about 0.1 cm³/g to about 3.0 cm³/g, about 0.1 cm³/g to about2.5 cm³/g, about 0.1 cm³/g to about 2.0 cm³/g, about 0.1 cm³/g to about1.9 cm³/g, about 0.1 cm³/g to about 1.8 cm³/g, about 0.1 cm³/g to about1.7 cm³/g, about 0.1 cm³/g to about 1.6 cm³/g, about 0.1 cm³/g to about1.5 cm³/g, about 0.1 cm³/g to about 1.4 cm³/g, about 0.1 cm³/g to about1.3 cm³/g, about 0.1 cm³/g to about 1.2 cm³/g, about 0.1 cm³/g to about1.1, about 0.1 cm³/g to about 1.0 cm³/g, about 0.1 cm³/g to about 0.9cm³/g, about 0.1 cm³/g to about 0.8 cm³/g, about 0.1 cm³/g to about 0.7cm³/g, about 0.1 cm³/g to about 0.6 cm³/g, about 0.1 cm³/g to about 0.5cm³/g, about 0.1 cm³/g to about 0.4 cm³/g, about 0.1 cm³/g to about 0.3cm³/g, about 0.1 cm³/g to about 0.2 cm³/g, 0.2 cm³/g to about 10.0cm³/g, about 0.2 cm³/g to about 7.0 cm³/g, about 0.2 cm³/g to about 6.0cm³/g, about 0.2 cm³/g to about 5.0 cm³/g, about 0.2 cm³/g to about 4.0cm³/g, about 0.2 cm³/g to about 3.5 cm³/g, about 0.2 cm³/g to about 3.0cm³/g, about 0.2 cm³/g to about 2.5 cm³/g, about 0.2 cm³/g to about 2.0cm³/g, about 0.2 cm³/g to about 1.9 cm³/g, about 0.2 cm³/g to about 1.8cm³/g, about 0.2 cm³/g to about 1.7 cm³/g, about 0.2 cm³/g to about 1.6cm³/g, about 0.2 cm³/g to about 1.5 cm³/g, about 0.2 cm³/g to about 1.4cm³/g, about 0.2 cm³/g to about 1.3 cm³/g, about 0.2 cm³/g to about 1.2cm³/g, about 0.2 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g,about 0.5 cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g,about 0.5 cm³/g to about 0.7 cm³/g, about 0.5 cm³/g to about 0.6 cm³/g,about 0.5 cm³/g to about 0.5 cm³/g, about 0.5 cm³/g to about 0.4 cm³/g,about 0.5 cm³/g to about 0.3 cm³/g, 0.5 cm³/g to about 10.0 cm³/g, about0.5 cm³/g to about 7.0 cm³/g, about 0.5 cm³/g to about 6.0 cm³/g, about0.5 cm³/g to about 5.0 cm³/g, about 0.5 cm³/g to about 4.0 cm³/g, about0.5 cm³/g to about 3.5 cm³/g, about 0.5 cm³/g to about 3.0 cm³/g, about0.5 cm³/g to about 2.5 cm³/g, about 0.5 cm³/g to about 2.0 cm³/g, about0.5 cm³/g to about 1.9 cm³/g, about 0.5 cm³/g to about 1.8 cm³/g, about0.5 cm³/g to about 1.7 cm³/g, about 0.5 cm³/g to about 1.6 cm³/g, about0.5 cm³/g to about 1.5 cm³/g, about 0.5 cm³/g to about 1.4 cm³/g, about0.5 cm³/g to about 1.3 cm³/g, about 0.5 cm³/g to about 1.2 cm³/g, about0.5 cm³/g to about 1.1, about 0.5 cm³/g to about 1.0 cm³/g, about 0.5cm³/g to about 0.9 cm³/g, about 0.5 cm³/g to about 0.8 cm³/g, about 0.5cm³/g to about 0.7 cm³/g, or about 0.5 cm³/g to about 0.6 cm³/g.

In a particular embodiment, the organosilica material can have a porevolume of about 0.1 cm³/g to about 5.0 cm³/g, particularly about 0.1cm³/g to about 3.0 cm³/g, particularly about 0.2 cm³/g to about 3.0cm³/g, particularly about 0.2 cm³/g to about 2.5 cm³/g, or particularlyabout 0.2 cm³/g to about 1.5 cm³/g.

III.F. Additional Metals

In some embodiments, the organosilica material can further comprise atleast one catalyst metal incorporated within the pores of theorganosilica material. Exemplary catalyst metals can include, but arenot limited to, a Group 6 element, a Group 8 element, a Group 9 element,a Group 10 element or a combination thereof. Exemplary Group 6 elementscan include, but are not limited to, chromium, molybdenum, and/ortungsten, particularly including molybdenum and/or tungsten. ExemplaryGroup 8 elements can include, but are not limited to, iron, ruthenium,and/or osmium. Exemplary Group 9 elements can include, but are notlimited to, cobalt, rhodium, and/or iridium, particularly includingcobalt. Exemplary Group 10 elements can include, but are not limited to,nickel, palladium and/or platinum.

The catalyst metal can be incorporated into the organosilica material byany convenient method, such as by impregnation, by ion exchange, or bycomplexation to surface sites. The catalyst metal so incorporated may beemployed to promote any one of a number of catalytic tranformationscommonly conducted in petroleum refining or petrochemicals production.Examples of such catalytic processes can include, but are not limitedto, hydrogenation, dehydrogenation, aromatization, aromatic saturation,hydrodesulfurization, olefin oligomerization, polymerization,hydrodenitrogenation, hydrocracking, naphtha reforming, paraffinisomerization, aromatic transalkylation, saturation of double/triplebonds, and the like, as well as combinations thereof.

Thus, in another embodiment, a catalyst material comprising theorganosilica material described herein is provided. The catalystmaterial may optionally comprise a binder or be self-bound. Suitablebinders, include but are not limited to active and inactive materials,synthetic or naturally occurring zeolites, as well as inorganicmaterials such as clays and/or oxides such as silica, alumina, zirconia,titania, silica-alumina, cerium oxide, magnesium oxide, or combinationsthereof. In particular, the binder may be silica-alumina, alumina and/ora zeolite, particularly alumina. Silica-alumina may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. It should be noted it is recognizedherein that the use of a material in conjunction with a zeolite bindermaterial, i.e., combined therewith or present during its synthesis,which itself is catalytically active may change the conversion and/orselectivity of the finished catalyst. It is also recognized herein thatinactive materials can suitably serve as diluents to control the amountof conversion if the present invention is employed in alkylationprocesses so that alkylation products can be obtained economically andorderly without employing other means for controlling the rate ofreaction. These inactive materials may be incorporated into naturallyoccurring clays, e.g., bentonite and kaolin, to improve the crushstrength of the catalyst under commercial operating conditions andfunction as binders or matrices for the catalyst. The catalystsdescribed herein typically can comprise, in a composited form, a ratioof support material to binder material of about 100 parts supportmaterial to about zero parts binder material; about 99 parts supportmaterial to about 1 parts binder material; about 95 parts supportmaterial to about 5 parts binder material. Additionally oralternatively, the catalysts described herein typically can comprise, ina composited form, a ratio of support material to binder materialranging from about 90 parts support material to about 10 parts bindermaterial to about 10 parts support material to about 90 parts bindermaterial; about 85 parts support material to about 15 parts bindermaterial to about 15 parts support material to about 85 parts bindermaterial; about 80 parts support material to 20 parts binder material to20 parts support material to 80 parts binder material, all ratios beingby weight, typically from 80:20 to 50:50 support material:bindermaterial, preferably from 65:35 to 35:65. Compositing may be done byconventional means including mulling the materials together followed byextrusion of pelletizing into the desired finished catalyst particles.

In some embodiments, the organosilica material can further comprisecationic metal sites incorporated into the network structure. Suchcationic metal sites may be incorporated by any convenient method, suchas impregnation or complexation to the surface, through an organicprecursor, or by some other method. This organometallic material may beemployed in a number of hydrocarbon separations conducted in petroleumrefining or petrochemicals production. Examples of such compounds to bedesirably separated from petrochemicals/fuels can include olefins,paraffins, aromatics, and the like.

Additionally or alternatively, the organosilica material can furthercomprise a surface metal incorporated within the pores of theorganosilica material. The surface metal can be selected from a Group 1element, a Group 2 element, a Group 13 element, and a combinationthereof. When a Group 1 element is present, it can preferably compriseor be sodium and/or potassium. When a Group 2 element is present, it caninclude, but may not be limited to, magnesium and/or calcium. When aGroup 13 element is present, it can include, but may not be limited to,boron and/or aluminum.

One or more of the Group 1, 2, 6, 8-10 and/or 13 elements may be presenton an exterior and/or interior surface of the organosilica material. Forexample, one or more of the Group 1, 2 and/or 13 elements may be presentin a first layer on the organosilica material and one or more of theGroup 6, 8, 9 and/or 10 elements may be present in a second layer, e.g.,at least partially atop the Group 1, 2 and/or 13 elements. Additionallyor alternatively, only one or more Group 6, 8, 9 and/or 10 elements maypresent on an exterior and/or interior surface of the organosilicamaterial. The surface metal(s) can be incorporated into/onto theorganosilica material by any convenient method, such as by impregnation,deposition, grafting, co-condensation, by ion exchange, and/or the like.

III. METHODS OF MAKING ORGANOSILICA MATERIALS

In another embodiment, methods of producing the organosilica materialdescribed herein are provided. The method comprises:

(a) providing an aqueous mixture that contains essentially no structuredirecting agent and/or porogen;

(b) adding at least one compound of Formula [R¹R²SiCH₂]₃ (Ia) into theaqueous mixture to form a solution, wherein each R¹ represents a C₁-C₄alkoxy group and R² represents a C₁-C₄ alkoxy group or a C₁-C₄ alkylgroup;

(c) adding at least one of the following:

-   -   (i) a compound of Formula R³OR⁴R⁵R⁶Si (IIa) wherein each R³ can        be a C₁-C₆ alkyl group, and R⁴, R⁵ and R⁶ each independently can        be selected from the group consisting of a C₁-C₆ alkyl group, a        C₁-C₆ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a        nitrogen-containing heteroaralkyl group, and a        nitrogen-containing optionally substituted heterocycloalkyl        group;    -   (ii) a compound of Formula Z¹⁹Z²⁰Z²¹Si—R⁷—Si Z¹⁹Z²⁰Z²¹ (IIIa),        wherein each Z¹⁹ independently can be a C₁-C₄ alkoxy group; Z²⁰        and Z²¹ each independently can be a C₁-C₄ alkoxy group or a        C₁-C₄ alkyl group; and R⁷ can be selected from the group        consisting a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a        C₂-C₈ alkynylene group, a nitrogen-containing C₂-C₁₀ alkylene        group, an optionally substituted C₆-C₂₀ aralkyl group, and an        optionally substituted C₄-C₂₀ heterocycloalkyl group; or    -   (iii) a combination thereof;

(d) aging the solution to produce a pre-product; and

(e) drying the pre-product to obtain an organosilica material which is apolymer comprising at least one independent monomer of Formula (I) asdescribed herein and at least one independent unit of Formulas (II),(III), (IV), (V) and/or (VI) as described herein.

III.A. Aqueous Mixture

The organosilica materials described herein may be made usingessentially no structure directing agent or porogen. Thus, the aqueousmixture contains essentially no added structure directing agent and/orno added porogen.

As used herein, “no added structure directing agent,” and “no addedporogen” means either (i) there is no component present in the synthesisof the organosilica material that aids in and/or guides thepolymerization and/or polycondensing and/or organization of the buildingblocks that form the framework of the organosilica material; or (ii)such component is present in the synthesis of the organosilica materialin a minor, or a non-substantial, or a negligible amount such that thecomponent cannot be said to aid in and/or guide the polymerizationand/or polycondensing and/or organization of the building blocks thatform the framework of the organosilica material. Further, “no addedstructure directing agent” is synonymous with “no added template” and“no added templating agent.”

1. Structure Directing Agent

Examples of a structure directing agent can include, but are not limitedto, non-ionic surfactants, ionic surfactants, cationic surfactants,silicon surfactants, amphoteric surfactants, polyalkylene oxidesurfactants, fluorosurfactants, colloidal crystals, polymers, hyperbranched molecules, star-shaped molecules, macromolecules, dendrimers,and combinations thereof. Additionally or alternatively, the surfacedirecting agent can comprise or be a poloxamer, a triblock polymer, atetraalkylammonium salt, a nonionic polyoxyethylene alkyl, a Geminisurfactant, or a mixture thereof. Examples of a tetraalkylammonium saltcan include, but are not limited to, cetyltrimethylammonium halides,such as cetyltrimethylammonium chloride (CTAC), cetyltrimethylammoniumbromide (CTAB), and octadecyltrimethylammonium chloride. Other exemplarysurface directing agents can additionally or alternatively includehexadecyltrimethylammonium chloride and/or cetylpyridinium bromide.

Poloxamers are block copolymers of ethylene oxide and propylene oxide,more particularly nonionic triblock copolymers composed of a centralhydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked bytwo hydrophilic chains of polyoxyethylene (poly(ethylene oxide)).Specifically, the term “poloxamer” refers to a polymer having theformula HO(C₂H₄))a(C₃H₆O)_(b)(C₂H₄O)_(a)H in which “a” and “b” denotethe number of polyoxyethylene and polyoxypropylene units, respectively.Poloxamers are also known by the trade name Pluronic®, for examplePluronic® 123 and Pluronic®F127. An additional triblock polymer isB50-6600.

Nonionic polyoxyethylene alkyl ethers are known by the trade name Brij®,for example Brij® 56, Brij® 58, Brij® 76, Brij® 78. Gemini surfactantsare compounds having at least two hydrophobic groups and at least one oroptionally two hydrophilic groups per molecule have been introduced.

2. Porogen

A porogen material is capable of forming domains, discrete regions,voids and/or pores in the organosilica material. An example of a porogenis a block copolymer (e.g., a di-block polymer). As used herein, porogendoes not include water. Examples of polymer porogens can include, butare not limited to, polyvinyl aromatics, such as polystyrenes,polyvinylpyridines, hydrogenated polyvinyl aromatics,polyacrylonitriles, polyalkylene oxides, such as polyethylene oxides andpolypropylene oxides, polyethylenes, polylactic acids, polysiloxanes,polycaprolactones, polycaprolactams, polyurethanes, polymethacrylates,such as polymethylmethacrylate or polymethacrylic acid, polyacrylates,such as polymethylacrylate and polyacrylic acid, polydienes such aspolybutadienes and polyisoprenes, polyvinyl chlorides, polyacetals, andamine-capped alkylene oxides, as well as combinations thereof.

Additionally or alternatively, porogens can be thermoplastichomopolymers and random (as opposed to block) copolymers. As usedherein, “homopolymer” means compounds comprising repeating units from asingle monomer. Suitable thermoplastic materials can include, but arenot limited to, homopolymers or copolymers of polystyrenes,polyacrylates, polymethacrylates, polybutadienes, polyisoprenes,polyphenylene oxides, polypropylene oxides, polyethylene oxides,poly(dimethylsiloxanes), polytetrahydrofurans, polyethylenes,polycyclohexylethylenes, polyethyloxazolines, polyvinylpyridines,polycaprolactones, polylactic acids, copolymers of these materials andmixtures of these materials. Examples of polystyrene include, but arenot limited to anionic polymerized polystyrene, syndiotacticpolystyrene, unsubstituted and substituted polystyrenes (for example,poly(α-methyl styrene)). The thermoplastic materials may be linear,branched, hyperbranched, dendritic, or star like in nature.

Additionally or alternatively, the porogen can be a solvent. Examples ofsolvents can include, but are not limited to, ketones (e.g.,cyclohexanone, cyclopentanone, 2-heptanone, cycloheptanone,cyclooctanone, cyclohexylpyrrolidinone, methyl isobutyl ketone, methylethyl ketone, acetone), carbonate compounds (e.g., ethylene carbonate,propylene carbonate), heterocyclic compounds (e.g.,3-methyl-2-oxazolidinone, dimethylimidazolidinone, N-methylpyrrolidone,pyridine), cyclic ethers (e.g., dioxane, tetrahydrofuran), chain ethers(e.g., diethyl ether, ethylene glycol dimethyl ether, propylene glycoldimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycoldimethyl ether, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, propylene glycol monomethyl ether (PGME), triethyleneglycol monobutyl ether, propylene glycol monopropyl ether, triethyleneglycol monomethyl ether, diethylene glycol ethyl ether, diethyleneglycol methyl ether, dipropylene glycol methyl ether, dipropylene glycoldimethyl ether, propylene glycol phenyl ether, tripropylene glycolmethyl ether), alcohols (e.g., methanol, ethanol), polyhydric alcohols(e.g., ethylene glycol, propylene glycol, polyethylene glycol,polypropylene glycol, glycerin, dipropylene glycol), nitrile compounds(e.g., acetonitrile, glutarodinitrile, methoxyacetonitrile,propionitrile, benzonitrile), esters (e.g., ethyl acetate, butylacetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethylethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate,2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate,propylene glycol monomethyl ether acetate (PGMEA), butyrolactone,phosphoric acid ester, phosphonic acid ester), aprotic polar substances(e.g., dimethyl sulfoxide, sulfolane, dimethylformamide,dimethylacetamide), nonpolar solvents (e.g., toluene, xylene,mesitylene), chlorine-based solvents (e.g., methylene dichloride,ethylene dichloride), benzene, dichlorobenzene, naphthalene, diphenylether, diisopropylbenzene, triethylamine, methyl benzoate, ethylbenzoate, butyl benzoate, monomethyl ether acetate hydroxy ethers suchas dibenzylethers, diglyme, triglyme, and mixtures thereof.

3. Base/Acid

In various embodiments, the aqueous mixture used in methods providedherein can comprise a base and/or an acid.

In certain embodiments where the aqueous mixture comprises a base, theaqueous mixture can have a pH from about 8 to about 15, from about 8 toabout 14.5, from about 8 to about 14, from about 8 to about 13.5, fromabout 8 to about 13, from about 8 to about 12.5, from about 8 to about12, from about 8 to about 11.5, from about 8 to about 11, from about 8to about 10.5, from about 8 to about 10, from about 8 to about 9.5, fromabout 8 to about 9, from about 8 to about 8.5, from about 8.5 to about15, from about 8.5 to about 14.5, from about 8.5 to about 14, from about8.5 to about 13.5, from about 8.5 to about 13, from about 8.5 to about12.5, from about 8.5 to about 12, from about 8.5 to about 11.5, fromabout 8.5 to about 11, from about 8.5 to about 10.5, from about 8.5 toabout 10, from about 8.5 to about 9.5, from about 8.5 to about 9, fromabout 9 to about 15, from about 9 to about 14.5, from about 9 to about14, from about 9 to about 13.5, from about 9 to about 13, from about 9to about 12.5, from about 9 to about 12, from about 9 to about 11.5,from about 9 to about 11, from about 9 to about 10.5, from about 9 toabout 10, from about 9 to about 9.5, from about 9.5 to about 15, fromabout 9.5 to about 14.5, from about 9.5 to about 14, from about 9.5 toabout 13.5, from about 9.5 to about 13, from about 9.5 to about 12.5,from about 9.5 to about 12, from about 9.5 to about 11.5, from about 9.5to about 11, from about 9.5 to about 10.5, from about 9.5 to about 10,from about 10 to about 15, from about 10 to about 14.5, from about 10 toabout 14, from about 10 to about 13.5, from about 10 to about 13, fromabout 10 to about 12.5, from about 10 to about 12, from about 10 toabout 11.5, from about 10 to about 11, from about 10 to about 10.5, fromabout 10.5 to about 15, from about 10.5 to about 14.5, from about 10.5to about 14, from about 10.5 to about 13.5, from about 10.5 to about 13,from about 10.5 to about 12.5, from about 10.5 to about 12, from about10.5 to about 11.5, from about 10.5 to about 11, from about 11 to about15, from about 11 to about 14.5, from about 11 to about 14, from about11 to about 13.5, from about 11 to about 13, from about 11 to about12.5, from about 11 to about 12, from about 11 to about 11.5, from about11.5 to about 15, from about 11.5 to about 14.5, from about 11.5 toabout 14, from about 11.5 to about 13.5, from about 11.5 to about 13,from about 11.5 to about 12.5, from about 11.5 to about 12, from about12 to about 15, from about 12 to about 14.5, from about 12 to about 14,from about 12 to about 13.5, from about 12 to about 13, from about 12 toabout 12.5, from about 12.5 to about 15, from about 12.5 to about 14.5,from about 12.5 to about 14, from about 12.5 to about 13.5, from about12.5 to about 13, from about 12.5 to about 15, from about 12.5 to about14.5, from about 12.5 to about 14, from about 12.5 to about 13.5, fromabout 12.5 to about 13, from about 13 to about 15, from about 13 toabout 14.5, from about 13 to about 14, from about 13 to about 13.5, fromabout 13.5 to about 15, from about 13.5 to about 14.5, from about 13.5to about 14, from about 14 to about 15, from about 14 to about 14.5, andfrom about 14.5 to about 15.

In a particular embodiment comprising a base, the pH can be from about 9to about 15, from about 9 to about 14 or from about 8 to about 14.

Exemplary bases can include, but are not limited to, sodium hydroxide,potassium hydroxide, lithium hydroxide, pyridine, pyrrole, piperazine,pyrrolidine, piperidine, picoline, monoethanolamine, diethanolamine,dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine,diazabicyclooctane, diazabicyclononane, diazabicycloundecene,tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia,ammonium hydroxide, methylamine, ethylamine, propylamine, butylamine,pentylamine, hexylamine, octylamine, nonylamine, decylamine,N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine,N,N-dibutylamine, trimethylamine, triethylamine, tripropylamine,tributylamine, cyclohexylamine, trimethylimidine,1-amino-3-methylbutane, dimethylglycine, 3-amino-3-methylamine, and thelike. These bases may be used either singly or in combination. In aparticular embodiment, the base can comprise or be sodium hydroxideand/or ammonium hydroxide.

In certain embodiments where the aqueous mixture comprises an acid, theaqueous mixture can have a pH from about 0.01 to about 6.0, from about0.01 to about 5, from about 0.01 to about 4, from about 0.01 to about 3,from about 0.01 to about 2, from about 0.01 to about 1, about 0.1 toabout 6.0, about 0.1 to about 5.5, about 0.1 to about 5.0, from about0.1 to about 4.8, from about 0.1 to about 4.5, from about 0.1 to about4.2, from about 0.1 to about 4.0, from about 0.1 to about 3.8, fromabout 0.1 to about 3.5, from about 0.1 to about 3.2, from about 0.1 toabout 3.0, from about 0.1 to about 2.8, from about 0.1 to about 2.5,from about 0.1 to about 2.2, from about 0.1 to about 2.0, from about 0.1to about 1.8, from about 0.1 to about 1.5, from about 0.1 to about 1.2,from about 0.1 to about 1.0, from about 0.1 to about 0.8, from about 0.1to about 0.5, from about 0.1 to about 0.2, about 0.2 to about 6.0, about0.2 to about 5.5, from about 0.2 to about 5, from about 0.2 to about4.8, from about 0.2 to about 4.5, from about 0.2 to about 4.2, fromabout 0.2 to about 4.0, from about 0.2 to about 3.8, from about 0.2 toabout 3.5, from about 0.2 to about 3.2, from about 0.2 to about 3.0,from about 0.2 to about 2.8, from about 0.2 to about 2.5, from about 0.2to about 2.2, from about 0.2 to about 2.0, from about 0.2 to about 1.8,from about 0.2 to about 1.5, from about 0.2 to about 1.2, from about 0.2to about 1.0, from about 0.2 to about 0.8, from about 0.2 to about 0.5,about 0.5 to about 6.0, about 0.5 to about 5.5, from about 0.5 to about5, from about 0.5 to about 4.8, from about 0.5 to about 4.5, from about0.5 to about 4.2, from about 0.5 to about 4.0, from about 0.5 to about3.8, from about 0.5 to about 3.5, from about 0.5 to about 3.2, fromabout 0.5 to about 3.0, from about 0.5 to about 2.8, from about 0.5 toabout 2.5, from about 0.5 to about 2.2, from about 0.5 to about 2.0,from about 0.5 to about 1.8, from about 0.5 to about 1.5, from about 0.5to about 1.2, from about 0.5 to about 1.0, from about 0.5 to about 0.8,about 0.8 to about 6.0, about 0.8 to about 5.5, from about 0.8 to about5, from about 0.8 to about 4.8, from about 0.8 to about 4.5, from about0.8 to about 4.2, from about 0.8 to about 4.0, from about 0.8 to about3.8, from about 0.8 to about 3.5, from about 0.8 to about 3.2, fromabout 0.8 to about 3.0, from about 0.8 to about 2.8, from about 0.8 toabout 2.5, from about 0.8 to about 2.2, from about 0.8 to about 2.0,from about 0.8 to about 1.8, from about 0.8 to about 1.5, from about 0.8to about 1.2, from about 0.8 to about 1.0, about 1.0 to about 6.0, about1.0 to about 5.5, from about 1.0 to about 5.0, from about 1.0 to about4.8, from about 1.0 to about 4.5, from about 1.0 to about 4.2, fromabout 1.0 to about 4.0, from about 1.0 to about 3.8, from about 1.0 toabout 3.5, from about 1.0 to about 3.2, from about 1.0 to about 3.0,from about 1.0 to about 2.8, from about 1.0 to about 2.5, from about 1.0to about 2.2, from about 1.0 to about 2.0, from about 1.0 to about 1.8,from about 1.0 to about 1.5, from about 1.0 to about 1.2, about 1.2 toabout 6.0, about 1.2 to about 5.5, from about 1.2 to about 5.0, fromabout 1.2 to about 4.8, from about 1.2 to about 4.5, from about 1.2 toabout 4.2, from about 1.2 to about 4.0, from about 1.2 to about 3.8,from about 1.2 to about 3.5, from about 1.2 to about 3.2, from about 1.2to about 3.0, from about 1.2 to about 2.8, from about 1.2 to about 2.5,from about 1.2 to about 2.2, from about 1.2 to about 2.0, from about 1.2to about 1.8, from about 1.2 to about 1.5, about 1.5 to about 6.0, about1.5 to about 5.5, from about 1.5 to about 5.0, from about 1.5 to about4.8, from about 1.5 to about 4.5, from about 1.5 to about 4.2, fromabout 1.5 to about 4.0, from about 1.5 to about 3.8, from about 1.5 toabout 3.5, from about 1.5 to about 3.2, from about 1.5 to about 3.0,from about 1.5 to about 2.8, from about 1.5 to about 2.5, from about 1.5to about 2.2, from about 1.5 to about 2.0, from about 1.5 to about 1.8,about 1.8 to about 6.0, about 1.8 to about 5.5, from about 1.8 to about5.0, from about 1.8 to about 4.8, from about 1.8 to about 4.5, fromabout 1.8 to about 4.2, from about 1.8 to about 4.0, from about 1.8 toabout 3.8, from about 1.8 to about 3.5, from about 1.8 to about 3.2,from about 1.8 to about 3.0, from about 1.8 to about 2.8, from about 1.8to about 2.5, from about 1.8 to about 2.2, from about 1.8 to about 2.0,about 2.0 to about 6.0, about 2.0 to about 5.5, from about 2.0 to about5.0, from about 2.0 to about 4.8, from about 2.0 to about 4.5, fromabout 2.0 to about 4.2, from about 2.0 to about 4.0, from about 2.0 toabout 3.8, from about 2.0 to about 3.5, from about 2.0 to about 3.2,from about 2.0 to about 3.0, from about 2.0 to about 2.8, from about 2.0to about 2.5, from about 2.0 to about 2.2, about 2.2 to about 6.0, about2.2 to about 5.5, from about 2.2 to about 5.0, from about 2.2 to about4.8, from about 2.2 to about 4.5, from about 2.2 to about 4.2, fromabout 2.2 to about 4.0, from about 2.2 to about 3.8, from about 2.2 toabout 3.5, from about 2.2 to about 3.2, from about 2.2 to about 3.0,from about 2.2 to about 2.8, from about 2.2 to about 2.5, about 2.5 toabout 6.0, about 2.5 to about 5.5, from about 2.5 to about 5.0, fromabout 2.5 to about 4.8, from about 2.5 to about 4.5, from about 2.5 toabout 4.2, from about 2.5 to about 4.0, from about 2.5 to about 3.8,from about 2.5 to about 3.5, from about 2.5 to about 3.2, from about 2.5to about 3.0, from about 2.5 to about 2.8, from about 2.8 to about 6.0,about 2.8 to about 5.5, from about 2.8 to about 5.0, from about 2.8 toabout 4.8, from about 2.8 to about 4.5, from about 2.8 to about 4.2,from about 2.8 to about 4.0, from about 2.8 to about 3.8, from about 2.8to about 3.5, from about 2.8 to about 3.2, from about 2.8 to about 3.0,from about 3.0 to about 6.0, from about 3.5 to about 5.5, from about 3.0to about 5.0, from about 3.0 to about 4.8, from about 3.0 to about 4.5,from about 3.0 to about 4.2, from about 3.0 to about 4.0, from about 3.0to about 3.8, from about 3.0 to about 3.5, from about 3.0 to about 3.2,from about 3.2 to about 6.0, from about 3.2 to about 5.5, from about 3.2to about 5, from about 3.2 to about 4.8, from about 3.2 to about 4.5,from about 3.2 to about 4.2, from about 3.2 to about 4.0, from about 3.2to about 3.8, from about 3.2 to about 3.5, from about 3.5 to about 6.0,from about 3.5 to about 5.5, from about 3.5 to about 5, from about 3.5to about 4.8, from about 3.5 to about 4.5, from about 3.5 to about 4.2,from about 3.5 to about 4.0, from about 3.5 to about 3.8, from about 3.8to about 5, from about 3.8 to about 4.8, from about 3.8 to about 4.5,from about 3.8 to about 4.2, from about 3.8 to about 4.0, from about 4.0to about 6.0, from about 4.0 to about 5.5, from about 4.0 to about 5,from about 4.0 to about 4.8, from about 4.0 to about 4.5, from about 4.0to about 4.2, from about 4.2 to about 5, from about 4.2 to about 4.8,from about 4.2 to about 4.5, from about 4.5 to about 5, from about 4.5to about 4.8, or from about 4.8 to about 5.

In a particular embodiment comprising an acid, the pH can be from about0.01 to about 6.0, about 0.2 to about 6.0, about 0.2 to about 5.0 orabout 0.2 to about 4.5.

Exemplary acids can include, but are not limited to, inorganic acidssuch as hydrochloric acid, nitric acid, sulfuric acid, hydrofluoricacid, phosphoric acid, boric acid and oxalic acid; and organic acidssuch as acetic acid, propionic acid, butanoic acid, pentanoic acid,hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoicacid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacicacid, gallic acid, butyric acid, mellitic acid, arachidonic acid,shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleicacid, linolenic acid, salicylic acid, benzoic acid, p-amino-benzoicacid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroaceticacid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid,formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid,citric acid, tartaric acid, succinic acid, itaconic acid, mesaconicacid, citraconic acid, malic acid, a hydrolysate of glutaric acid, ahydrolysate of maleic anhydride, a hydrolysate of phthalic anhydride,and the like. These acids may be used either singly or in combination.In a particular embodiment, the acid can comprise or be hydrochloricacid.

III.B. Compounds of Formula (Ia)

The methods provided herein comprise the step of adding at least onecompound of Formula [R¹R²SiCH₂]₃ (Ia) into the aqueous mixture to form asolution, wherein each R¹ represents a C₁-C₄ alkoxy group and each R²represents a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group.

In one embodiment, each R¹ can be a C₁-C₃ alkoxy or methoxy or ethoxy.

Additionally or alternatively, each R² can be a C₁-C₄ alkoxy, a C₁-C₃alkoxy or methoxy or ethoxy. Additionally or alternatively, each R² cancomprise methyl, ethyl or propyl, such as a methyl or ethyl.

Additionally or alternatively, each R¹ can be a C₁-C₂ alkoxy group andR² can be a C₁-C₂ alkoxy group or a C₁-C₂ alkyl group.

Additionally or alternatively, each R¹ can be methoxy or ethoxy and eachR² can be methyl or ethyl.

In a particular embodiment, R¹ and R² can be ethoxy, such that thecompound corresponding to Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, ([(EtO)₂SiCH₂]₃).

In a particular embodiment, R¹ can be ethoxy and R² can be methyl, suchthat compound corresponding to Formula (Ia) can be1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane,([EtOCH₃SiCH₂]₃).

In various aspects, more than one compound of Formula (Ia) (e.g., sameor different compound) may be added to the aqueous mixture to form asolution. For example, [(EtO)₂SiCH₂]₃ and [EtOCH₃SiCH₂]₃ may both beadded to the aqueous mixture to form a solution.

When more than one compound of Formula (Ia) is used, the respectivecompounds may be used in a wide variety of molar ratios. For example, iftwo compounds of Formula (Ia) are used, the molar ratio of each compoundmay vary from 1:99 to 99:1, such as from 10:90 to 90:10. The use ofdifferent compounds of Formula (Ia) allows to tailor the properties ofthe organosilica materials made by the process of the invention, as willbe further explained in the examples and in the section of thisspecification describing the properties of the organosilicas made by thepresent processes.

III.D. Compounds of Formula (IIa)

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a compound of FormulaR³OR⁴R⁵R⁶Si (IIa) to obtain an organosilica material which is acopolymer comprising at least one independent unit of Formula (I) asdescribed herein and at least one independent unit of Formulas (II),(IV), and/or (V) as described herein, wherein each R³ can be a C₁-C₆alkyl group, and R⁴, R⁵ and R⁶ each independently can be selected fromthe group consisting of a C₁-C₆ alkyl group, a C₁-C₆ alkoxy group, anitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containingheteroaralkyl group, and a nitrogen-containing optionally substitutedheterocycloalkyl group.

In one embodiment, each R³ can be a C₁-C₆ alkyl group, and R⁴, R⁵ and R⁶each independently can be selected from the group consisting of a C₁-C₆alkyl group and a C₁-C₆ alkoxy group.

In various embodiments, each R³ can be a C₁-C₅ alkyl group, a C₁-C₄alkyl group, a C₁-C₃ alkyl group, a C₁-C₂ alkyl group, or methyl. Inparticular, each R³ can be methyl or ethyl.

Additionally or alternatively, R⁴, R⁵ and R⁶ can be each independently aC₁-C₅ alkyl group, a C₁-C₄ alkyl group, a C₁-C₃ alkyl group, a C₁-C₂alkyl group, or methyl.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a C₁-C₂ alkyl group.

Additionally or alternatively, R⁴, R⁵ and R⁶ can be each independently aC₁-C₅ alkoxy group, a C₁-C₄ alkoxy group, a C₁-C₃ alkoxy group, a C₁-C₂alkoxy group, or methoxy.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a C₁-C₂ alkoxy group.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a C₁-C₂ alkyl group or a C₁-C₂alkoxy group.

Additionally or alternatively, R⁴, R⁵ and R⁶ can be each independently anitrogen-containing C₁-C₉ alkyl group, a nitrogen-containing C₁-C₈ alkylgroup, a nitrogen-containing C₁-C₇ alkyl group, a nitrogen-containingC₁-C₆ alkyl group, a nitrogen-containing C₁-C₅ alkyl group, anitrogen-containing C₁-C₄ alkyl group, a nitrogen-containing C₁-C₃ alkylgroup, a nitrogen-containing C₁-C₂ alkyl group, or a methylamine. Inparticular, R⁴, R⁵ and R⁶ can be each independently anitrogen-containing C₂-C₁₀ alkyl group, a nitrogen-containing C₃-C₁₀alkyl group, a nitrogen-containing C₃-C₉ alkyl group, or anitrogen-containing C₃-C₈ alkyl group. The aforementionednitrogen-containing alkyl groups may have one or more nitrogen atoms(e.g., 2, 3, etc.). Examples of nitrogen-containing C₁-C₁₀ alkyl groupsinclude, but are not limited to,

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a nitrogen-containing C₃-C₈alkyl group.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group or a nitrogen-containing C₃-C₈ alkyl group.

Additionally or alternatively, R⁴, R⁵ and R⁶ can be each independently anitrogen-containing heteroaralkyl group. The nitrogen-containingheteroaralkyl group can be a nitrogen-containing C₄-C₁₂ heteroaralkylgroup, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or anitrogen-containing C₄-C₈ heteroaralkyl group. Examples ofnitrogen-containing heteroaralkyl groups include but are not limited topyridinylethyl, pyridinylpropyl, pyridinylmethyl, indolylmethyl,pyrazinylethyl, and pyrazinylpropyl. The aforementionednitrogen-containing heteroaralkyl groups may have one or more nitrogenatoms (e.g., 2, 3, etc.).

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a nitrogen-containingheteroaralkyl group.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈ alkyl group or anitrogen-containing heteroaralkyl group.

Additionally or alternatively, R⁴, R⁵ and R⁶ can be each independently anitrogen-containing heterocycloalkyl group, wherein the heterocycloalkylgroup may be optionally substituted with a C₁-C₆ alkyl group,particularly a C₁-C₄ alkyl group. The nitrogen-containingheterocycloalkyl group can be a nitrogen-containing C₄-C₁₂heterocycloalkyl group, a nitrogen-containing C₄-C₁₀ heterocycloalkylgroup, or a nitrogen-containing C₄-C₈ heterocycloalkyl group. Examplesof nitrogen-containing heterocycloalkyl groups include but are notlimited to piperazinylethyl, piperazinylpropyl, piperidinylethyl,piperidinylpropyl. The aforementioned nitrogen-containingheterocycloalkyl groups may have one or more nitrogen atoms (e.g., 2, 3,etc.).

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a nitrogen-containing optionallysubstituted heterocycloalkyl group.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a C₁-C₂ alkyl group, a C₁-C₂alkoxy group, a nitrogen-containing C₃-C₈ alkyl group, anitrogen-containing heteroaralkyl group, or a nitrogen-containingoptionally substituted heterocycloalkyl group.

Additionally or alternatively, each R³ can be a C₁-C₂ alkyl group andR⁴, R⁵ and R⁶ can be each independently a C₁-C₂ alkyl group, C₁-C₂alkoxy group, a nitrogen-containing C₃-C₁₀ alkyl group, anitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containingoptionally substituted C₄-C₁₀ heterocycloalkyl group.

In a particular embodiment, each R³ can be ethyl and R⁴, R⁵ and R⁶ canbe ethoxy, such that the compound corresponding to Formula (IIa) can betetraethyl orthosilicate (TEOS) ((EtO)₄Si).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃), acompound of Formula (IIa) can be tetraethyl orthosilicate (TEOS)((EtO)₄Si).

In another particular embodiment, each R³ can be ethyl, R⁴ can be methyland R⁵ and R⁶ can be ethoxy, such that the compound corresponding toFormula (IIa) can be methyltriethoxysilane (MTES) ((EtO)₃CH₃Si).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃ and acompound of Formula (IIa) can be methyltriethoxysilane (MTES)((EtO)₃CH₃₋Si).

In another particular embodiment, a compound of Formula (Ia) can be1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane ([EtOCH₃SiCH₂]₃and a compound of Formula (IIa) can be tetraethyl orthosilicate (TEOS)((EtO)₄Si).

In another particular embodiment, R³ can be ethyl, R⁴ and R⁵ can beethoxy and R⁶ can be

such that the compound corresponding to Formula (IIa) can be(3-aminopropyl)triethoxysilane (H₂N(CH₂)₃(EtO)₃Si).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIa) can be (3-aminopropyl)triethoxysilane(H₂N(CH₂)₃(EtO)₃Si).

In another particular embodiment, R³ can be methyl, R⁴ and R⁵ can bemethoxy and R⁴ can be

such that the compound corresponding to Formula (IIa) can be(N,N-dimethylaminopropyl)trimethoxysilane (((CH₃)₂N(CH₂)₃)(MeO)₃Si).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIa) can be(N,N-dimethylaminopropyl)trimethoxysilane (((CH₃)₂N(CH₂)₃)(MeO)₃Si).

In another particular embodiment, R³ can be ethyl, R⁴ and R⁵ can beethoxy and R⁶ can be

such that the compound corresponding to Formula (IIa) can be(N-(2-aminoethyl)-3-aminopropyltriethoxysilane ((H₂N(CH₂)₂NH(CH₂)₃)(EtO)₂Si).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIa) can be(N-(2-aminoethyl)-3-aminopropyltriethoxysilane ((H₂N(CH₂)₂NH(CH₂)₃)(EtO)₂Si).

In another particular embodiment, R³ can be ethyl, R⁴ and R⁵ can beethoxy and R⁶ can be

such that the compound corresponding to Formula (IIa) can be4-methyl-1-(3-triethoxysilylpropyl)-piperazine.

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIa) can be4-methyl-1-(3-triethoxysilylpropyl)-piperazine.

In another particular embodiment, R³ can be ethyl, R⁴ and R⁵ can beethoxy and R⁶ can be

such that the compound corresponding to Formula (IIa) can be4-(2-(triethoxysily)ethyl)pyridine.

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIa) can be 4-(2-(triethoxysily)ethyl)pyridine.

In another particular embodiment, R³ can be ethyl, R⁴ and R⁵ can beethoxy and R⁵ can be

such that the compound corresponding to Formula (IIa) can be1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole.

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIa) can be1-(3-(triethoxysilyl)propyl)-4,5-dihydro-1H-imidazole.

The molar ratio of compound of Formula (Ia) to compound of Formula (IIa)may vary within wide limits, such as from about 99:1 to about 1:99, fromabout 1:5 to about 5:1, from about 4:1 to about 1:4 or from about 3:2 toabout 2:3. For example, a molar ratio of compound of Formula (Ia) tocompound of Formula (IIa) can be from about 4:1 to 1:4 or from about2.5:1 to about 1:2.5, about 2:1 to about 1:2, such as about 1.5:1 toabout 1.5:1.

III.D. Compounds of Formula (IIIa)

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a compound of FormulaZ¹⁹Z²⁰Z²¹Si—R⁷—Si Z¹⁹Z²⁰Z²¹ (IIIa) to obtain an organosilica materialwhich is a copolymer comprising at at least one independent unit Formula(I) as described herein and at least one independent unit of Formulas(III), (IV) and/or (VI) as described herein, wherein each Z¹⁹independently can be a C₁-C₄ alkoxy group; Z²⁰ and Z²¹ eachindependently can be a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group; andeach R⁷ can be selected from the group consisting a C₁-C₈ alkylenegroup, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, anitrogen-containing C₂-C₁₀ alkylene group, an optionally substitutedC₆-C₂₀ aralkyl group, and an optionally substituted C₄-C₂₀heterocycloalkyl group.

In one embodiment, each Z¹⁹ can be a C₁-C₄ alkoxy group; Z²⁰ and Z²¹each independently can be a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group;and R⁷ can be selected from the group consisting a C₁-C₈ alkylene group,a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group, an optionallysubstituted C₆-C₂₀ aralkyl group, and an optionally substituted C₄-C₂₀heterocycloalkyl group.

In another embodiment, each Z¹⁹ can be a C₁-C₄ alkoxy group; Z²⁰ and Z²¹each independently can be a C₁-C₄ alkoxy group or a C₁-C₄ alkyl group;and each R⁷ can be a nitrogen-containing C₂-C₁₀ alkylene group.

In various embodiments, each Z¹⁹ can be a C₁-C₃ alkoxy group, a C₁-C₂alkoxy group, or methoxy.

Additionally or alternatively, Z²⁰ and Z²¹ each independently can be aC₁-C₃ alkoxy group, a C₁-C₂ alkoxy group, or methoxy.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group andZ²⁰ and Z²¹ each independently can be a C₁-C₂ alkoxy group.

Additionally or alternatively, Z²⁰ and Z²¹ each independently can be aC₁-C₃ alkyl group, a C₁-C₂ alkyl group, or methyl.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group andZ²⁰ and Z²¹ each independently can be a C₁-C₂ alkyl group.

Additionally or alternatively, Z¹⁹ can be a C₁-C₂ alkoxy group and Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup.

Additionally or alternatively, each R⁷ can be a C₁-C₇ alkylene group, aC₁-C₆ alkylene group, a C₁-C₅ alkylene group, a C₁-C₄ alkylene group, aC₁-C₃ alkylene group, a C₁-C₂ alkylene group, or —CH₂—.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₁-C₂ alkylene group.

Additionally or alternatively, each R⁷ can be a C₂-C₇ alkenylene group,a C₁-C₆ alkenylene group, a C₂-C₅ alkenylene group, a C₂-C₄ a alkenylenegroup, a C₂-C₃ alkenylene group, or —CH═CH—.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₁-C₂ alkenylene group.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₁-C₂ alkylene group or a C₁-C₂ alkenylenegroup.

Additionally or alternatively, each R⁷ can be a C₂-C₇ alkynylene group,a C₁-C₆ alkynylene group, a C₂-C₅ alkynylene group, a C₂-C₄ a alkynylenegroup, a C₂-C₃ alkynylene group, or —C≡C—.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and R⁷ can be a C₂-C₄ alkynylene group.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup or a C₂-C₄ alkynylene group.

Additionally or alternatively, each R⁷ can be a nitrogen-containingC₂-C₁₀ alkylene group, a nitrogen-containing C₃-C₁₀ alkylene group, anitrogen-containing C₄-C₁₀ alkylene group, a nitrogen-containing C₄-C₉alkylene group, a nitrogen-containing C₄-C₈ alkylene group, or nitrogencontaining C₃-C₈ alkylene group. The aforementioned nitrogen-containingalkylene groups may have one or more nitrogen atoms (e.g., 2, 3, etc.).Examples of nitrogen-containing alkylene groups include, but are notlimited to,

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a nitrogen-containing C₄-C₁₀ alkylene group.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup, a C₂-C₄ alkynylene group or a nitrogen-containing C₄-C₁₀ alkylenegroup.

Additionally or alternatively, each R⁷ can be an optionally substitutedC₆-C₂₀ aralkyl, an optionally substituted C₆-C₁₄ aralkyl, or anoptionally substituted C₆-C₁₀ aralkyl. Examples of C₆-C₂₀ aralkylsinclude, but are not limited to, phenymethyl, phenylethyl, andnaphthylmethyl. The aralkyl may be optionally substituted with a C₁-C₆alkyl group, particularly a C₁-C₄ alkyl group.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be an optionally substituted C₆-C₁₀ aralkyl.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup, a C₂-C₄ alkynylene group, or an optionally substituted C₆-C₁₀aralkyl.

Additionally or alternatively, R⁷ can be an optionally substitutedC₄-C₂₀ heterocycloalkyl group, an optionally substituted C₄-C₁₆heterocycloalkyl group, an optionally substituted C₄-C₁₂heterocycloalkyl group, or an optionally substituted C₄-C₁₀heterocycloalkyl group. Examples of C₄-C₂₀ heterocycloalkyl groupsinclude, but are not limited to, thienylmethyl, furylethyl,pyrrolylmethyl, piperazinylethyl, pyridylmethyl, benzoxazolylethyl,quinolinylpropyl, and imidazolylpropyl. The heterocycloalkyl may beoptionally substituted with a C₁-C₆ alkyl group, particularly a C₁-C₄alkyl group.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and R⁷ can be an optionally substituted C₄-C₁₂ heterocycloalkylgroup.

Additionally or alternatively, each Z¹⁹ can be a C₁-C₂ alkoxy group; Z²⁰and Z²¹ each independently can be a C₁-C₂ alkoxy group or a C₁-C₂ alkylgroup; and each R⁷ can be a C₂-C₄ alkylene group, a C₂-C₄ alkenylenegroup, a C₂-C₄ alkynylene group, an optionally substituted C₆-C₁₀aralkyl, or an optionally substituted C₄-C₁₂ heterocycloalkyl group.

In a particular embodiment, Z¹⁹ and Z²⁰ can be ethoxy, Z²¹ can be methyland R⁷ can be —CH₂CH₂—, such that compound corresponding to Formula(IIIa) can be 1,2-bis(methyldiethoxysilyl)ethane(CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃), and acompound of Formula (IIIa) can be 1,2-bis(methyldiethoxysilyl)ethane(CH₃ (EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃).

In another particular embodiment, Z¹⁹, Z²⁰ and Z²¹ can be ethoxy and R⁷can be —CH₂—, such that compound corresponding to Formula (IIIa) can bebis(triethoxysilyl)methane ((EtO)₃Si—CH₂—Si(EtO)₃).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIIa) can be bis(triethoxysilyl)methane((EtO)₃Si—CH₂—Si(EtO)₃).

In another particular embodiment, Z¹⁹, Z²⁰ and Z²¹ can be ethoxy and R⁷can be —HC═CH—, such that compound corresponding to Formula (IIIa) canbe 1,2-bis(triethoxysilyl)ethylene ((EtO)₃Si—HC═CH—Si(EtO)₃).

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃)) and acompound of Formula (IIIa) can be 1,2-bis(triethoxysilyl)ethylene((EtO)₃Si—HC═CH—Si(EtO)₃).

In another particular embodiment, a compound of Formula (IIIa) can bebis(triethoxysilyl)methane ((EtO)₃Si—CH₂—Si(EtO)₃) and a compound ofFormula (IIa) can be tetraethyl orthosilicate (TEOS) ((EtO)₄Si).

In a particular embodiment, Z¹⁹, Z²⁰ and Z²¹ can be methoxy and R⁷ canbe

such that compound corresponding to Formula (IIIa) can beN,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine.

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIIa) can beN,N′-bis[(3-trimethoxysilyl)propyl]ethylenediamine.

In another particular embodiment, Z¹⁹ and Z²⁰ can be ethoxy, Z²¹ can bemethyl and R⁷ can be

such that compound corresponding to Formula (IIIa) can bebis[(methyldiethoxysilyl)propyl]amine.

In another particular embodiment, a compound of a compound of Formula(Ia) can be 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane([(EtO)₂SiCH₂]₃) and a compound of Formula (IIIa) can bebis[(methyldiethoxysilyl)propyl]amine.

In another particular embodiment, Z¹⁹ and Z²⁰ can be methoxy, Z²¹ can bemethyl and R⁷ can be

such that compound corresponding to Formula (IIIa) can bebis[(methyldimethoxysilyl)propyl]-N-methylamine.

In another particular embodiment, a compound of Formula (Ia) can be1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) and acompound of Formula (IIIa) can bebis[(methyldimethoxysilyl)propyl]-N-methylamine.

The molar ratio of compound of Formula (Ia) to compound of Formula(IIIa) may vary within wide limits, such as from about 99:1 to about1:99, from about 1:5 to about 5:1, from about 4:1 to about 1:4 or fromabout 3:2 to about 2:3. For example, a molar ratio of compound ofFormula (Ia) to compound of Formula (IIIa) can be from about 4:1 to 1:4or from about 2.5:1 to 1:2.5, about 2:1 to about 1:2, such as about1.5:1 to about 1.5:1.

III.C. Metal Chelate Sources

In additional embodiments, the methods provided herein can furthercomprise adding to the aqueous solution a source of metal chelatecompounds.

Examples of metal chelate compounds, when present, can include titaniumchelate compounds such as triethoxy.mono(acetylacetonato) titanium,tri-n-propoxy.mono(acetylacetonato)titanium, tri-i-propoxy.mono(acetylacetonato)titanium,tri-n-butoxy.mono(acetylacetonato)titanium,tri-sec-butoxy.mono(acetylacetonato)titanium,tri-t-butoxy.mono(acetylacetonato)titanium,diethoxy.bis(acetylacetonato)titanium,di-n-propoxy.bis(acetylacetonato)titanium,di-i-propoxy.bis(acetylacetonato)titanium,di-n-butoxy.bis(acetylacetonato)titanium,di-sec-butoxy.bis(acetylacetonato)titanium,di-t-butoxy.bis(acetylacetonato)titanium,monoethoxy.tris(acetylacetonato)titanium,mono-n-propoxy.tris(acetylacetonato) titanium,mono-i-propoxy.tris(acetylacetonato)titanium, mono-n-butoxy.tris(acetylacetonato)titanium,mono-sec-butoxy.tris(acetylacetonato)titanium,mono-t-butoxy-tris(acetylacetonato)titanium,tetrakis(acetylacetonato)titanium, triethoxy.mono(ethylacetoacetaato)titanium,tri-n-propoxy.mono(ethylacetoacetato)titanium,tri-i-propoxy.mono(ethylacetoacetato) titanium,tri-n-butoxy.mono(ethylacetoacetato) titanium,tri-sec-butoxy.mono(ethylacetoacetato) titanium,tri-t-butoxy-mono(ethylacetoacetato)titanium,diethoxy.bis(ethylacetoacetato)titanium,di-n-propoxy.bis(ethylacetoacetato)titanium,di-i-propoxy.bis(ethylacetoacetato)titanium,di-n-butoxy.bis(ethylacetoacetato)titanium,di-sec-butoxy.bis(ethylacetoacetato)titanium,di-t-butoxy.bis(ethylacetoacetato)titanium,monoethoxy.tris(ethylacetoacetato)titanium,mono-n-propoxy.tris(ethylacetoaetato)titanium,mono-i-propoxy.tris(ethylacetoacetato) titanium,mono-n-butoxy.tris(ethylacetoacetato)titanium, mono-sec-butoxy.tris(ethylacetoacetato)titanium,mono-t-butoxy.tris(ethylacetoacetato)titanium,tetrakis(ethylacetoacetato)titanium,mono(acetylacetonato)tris(ethylacetoacetato) titanium,bis(acetylacetonato)bis(ethylacetoacetato)titanium, andtris(acetylacetonato)mono(ethylacetoacetato)titanium; zirconium chelatecompounds such as triethoxy.mono(acetylacetonato)zirconium,tri-n-propoxy.mono(acetylacetonato) zirconium,tri-i-propoxy.mono(acetylacetonato)zirconium, tri-n-butoxy.mono(acetylacetonato)zirconium,tri-sec-butoxy.mono(acetylacetonato)zirconium,tri-t-butoxy.mono(acetylacetonato)zirconium,diethoxy.bis(acetylacetonato)zirconium,di-n-propoxy.bis(acetylacetonato)zirconium,di-i-propoxy.bis(acetylacetonato)zirconium,di-n-butoxy.bis(acetylacetonato)zirconium,di-sec-butoxy.bis(acetylacetonato)zirconium,di-t-butoxy.bis(acetylacetonato)zirconium,monoethoxy.tris(acetylacetonato)zirconium,mono-n-propoxy.tris(acetylacetonato)zirconium,mono-i-propoxy.tris(acetylacetonato) zirconium,mono-n-butoxy.tris(acetylacetonato)zirconium, mono-sec-butoxy.tris(acetylacetonato)zirconium,mono-t-butoxy.tris(acetylacetonato)zirconium,tetrakis(acetylacetonato)zirconium,triethoxy.mono(ethylacetoacetato)zirconium,tri-n-propoxy.mono(ethylacetoacetato)zirconium,tri-i-propoxy.mono(ethylacetoacetato) zirconium,tri-n-butoxy.mono(ethylacetoacetato)zirconium, tri-sec-butoxy.mono(ethylacetoacetato)zirconium,tri-t-butoxy.mono(ethylacetoacetato)zirconium,diethoxy.bis(ethylacetoacetato)zirconium,di-n-propoxy.bis(ethylacetoacetato)zirconium,di-i-propoxy.bis(ethylacetoacetato)zirconium,di-n-butoxy.bis(ethylacetoacetato) zirconium,di-sec-butoxy.bis(ethylacetoacetato)zirconium, di-t-butoxy.bis(ethylacetoacetato)zirconium,monoethoxy.tris(ethylacetoacetato)zirconium,mono-n-propoxy.tris(ethylacetoacetato)zirconium,mono-i-propoxy.tris(ethylacetoacetato) zirconium,mono-n-butoxy.tris(ethylacetoacetato)zirconium, mono-sec-butoxy.tris(ethylacetoacetato)zirconium,mono-t-butoxy.tris(ethylacetoacetato)zirconium,tetrakis(ethylacetoacetato)zirconium,mono(acetylacetonato)tris(ethylacetoacetato) zirconium,bis(acetylacetonato)bis(ethylacetoacetato)zirconium, andtris(acetylacetonato)mono(ethylacetoacetato)zirconium; and aluminumchelate compounds such as tris(acetylacetonato)aluminum andtris(ethylacetoacetato)aluminum. Of these, the chelate compounds oftitanium or aluminum can be of note, of which the chelate compounds oftitanium can be particularly of note. These metal chelate compounds maybe used either singly or in combination.

III.D. Molar Ratio

In the methods described herein, a molar ratio of Formula (Ia):Formula(IIa), Formula (Ia):Formula (IIIa) of about 99:1 to about 1:99, about75:1 to about 1:99, about 50:1 to about 1:99, about 25:1 to about 1:99,about 15:1 to about 1:99, about 50:1 to about 1:50, about 25:1 to about1:25 or about 15:1 to about 1:15 may be used. For example, molar ratiosof about 3:2, about 4:1, about 4:3, about 5:1, about 2:3, about 1:1about 5:2 and about 15:1 may be used. For example a molar ratio ofFormula (Ia):Formula (IIa), Formula (Ia):Formula (IIIa) of about 3:2,about 4:1, about 4:3, about 2:3, about 1:1 and about 5:2 may be used.For example, a molar ratio of Formula (Ia):Formula (IIa) can be about2:3, about 4:3, about 4:1 or about 3:2. A molar ratio of Formula(Ia):Formula (IIIa) can be about 2:3, and about 4:1. A molar ratio ofFormula (III):Formula (II) can be about 5:2, about 1:1, about 1:2 orabout 2:3.

For the sake of the following discussion, the compounds of Formula (Ia),(IIa) and (IIIa) shall be referred to collectively as starting siloxane.Depending on the choice of starting materials, the solution may have avariety of compositions. For example, if base is used, the solution mayhave molar ratios of starting siloxane to OH⁻ of from about 1:5 to about1:20, such as from about 1:5 to about 1:15 or from about 1:5 to 1:10, orfrom about 1:6 to 1:20. If acid is used, the solution may have molarratios of starting siloxane:H⁺ of from about 50:1 to about 5:1, such asfrom about 45:1 to about 10:1. In both cases when acid or base is used,the molar ratios of starting siloxane to H₂O may vary from about 1:50 toabout 1:1000, such as from about 1:100 to about 1:500.

III.E. Aging the Solution

The solution formed in the methods described herein can be aged for atleast about 4 hours, at least about 6 hours, at least about 12 hours, atleast about 18 hours, at least about 24 hours (1 day), at least about 30hours, at least about 36 hours, at least about 42 hours, at least about48 hours (2 days), at least about 54 hours, at least about 60 hours, atleast about 66 hours, at least about 72 hours (3 days), at least about96 hours (4 days), at least about 120 hours (5 days) or at least about144 hours (6 days).

Additionally or alternatively, the solution formed in the methodsdescribed herein can be aged for about 4 hours to about 144 hours (6days), about 4 hours to about 120 hours (5 days), about 4 hours to about96 hours (4 days), about 4 hours to about 72 hours (3 days), about 4hours to about 66 hours, about 4 hours to about 60 hours, about 4 hoursto about 54 hours, about 4 hours to about 48 hours (2 days), about 4hours to about 42 hours, about 4 hours to about 36 hours, about 4 hoursto about 30 hours, about 4 hours to about 24 hours (1 day), about 4hours to about 18 hours, about 4 hours to about 12 hours, about 4 hoursto about 6 hours, about 6 hours to about 144 hours (6 days), about 6hours to about 120 hours (5 days), about 6 hours to about 96 hours (4days), about 6 hours to about 72 hours (3 days), about 6 hours to about66 hours, about 6 hours to about 60 hours, about 6 hours to about 54hours, about 6 hours to about 48 hours (2 days), about 6 hours to about42 hours, about 6 hours to about 36 hours, about 6 hours to about 30hours, about 6 hours to about 24 hours (1 day), about 6 hours to about18 hours, about 6 hours to about 12 hours, about 12 hours to about 144hours (6 days), about 12 hours to about 120 hours (5 days), about 12hours to about 96 hours (4 days), about 12 hours to about 72 hours (3days), about 12 hours to about 66 hours, about 12 hours to about 60hours, about 12 hours to about 54 hours, about 12 hours to about 48hours (2 days), about 12 hours to about 42 hours, about 12 hours toabout 36 hours, about 12 hours to about 30 hours, about 12 hours toabout 24 hours (1 day), about 12 hours to about 18 hours, about 18 hoursto about 144 hours (6 days), about 18 hours to about 120 hours (5 days),about 18 hours to about 96 hours (4 days), about 18 hours to about 72hours (3 days), about 18 hours to about 66 hours, about 18 hours toabout 60 hours, about 18 hours to about 54 hours, about 18 hours toabout 48 hours (2 days), about 18 hours to about 42 hours, about 18hours to about 36 hours, about 18 hours to about 30 hours, about 18hours to about 24 hours (1 day), about 24 hours (1 day) to about 144hours (6 days), about 24 (1 day) hours (1 day) to about 120 hours (5days), about 24 hours (1 day) to about 96 hours (4 days), about 24 hours(1 day) to about 72 hours (3 days), about 24 hours (1 day) to about 66hours, about 24 hours (1 day) to about 60 hours, about 24 hours (1 day)to about 54 hours, about 24 hours (1 day) to about 48 hours (2 days),about 24 hours (1 day) to about 42 hours, about 24 hours (1 day) toabout 36 hours, about 24 hours (1 day) to about 30 hours, about 30 hoursto about 144 hours (6 days), about 30 hours to about 120 hours (5 days),about 30 hours to about 96 hours (4 days), about 30 hours to about 72hours (3 days), about 30 hours to about 66 hours, about 30 hours toabout 60 hours, about 30 hours to about 54 hours, about 30 hours toabout 48 hours (2 days), about 30 hours to about 42 hours, about 30hours to about 36 hours, about 36 hours to about 144 hours (6 days),about 36 hours to about 120 hours (5 days), about 36 hours to about 96hours (4 days), about 36 hours to about 72 hours (3 days), about 36hours to about 66 hours, about 36 hours to about 60 hours, about 36hours to about 54 hours, about 36 hours to about 48 hours (2 days),about 36 hours to about 42 hours, about 42 hours to about 144 hours (6days), about 42 hours to about 120 hours (5 days), about 42 hours toabout 96 hours (4 days), about 42 hours to about 72 hours (3 days),about 42 hours to about 66 hours, about 42 hours to about 60 hours,about 42 hours to about 54 hours, about 42 hours to about 48 hours (2days), about 48 hours (2 days) to about 144 hours (6 days), about 48hours (2 days) to about 120 hours (5 days), about 48 hours (2 days) toabout 96 hours (4 days), about 48 hours (2 days) to about 72 hours (3days), about 48 hours (2 days) to about 66 hours, about 48 hours (2days) to about 60 hours, about 48 hours (2 days) to about 54 hours,about 54 hours to about 144 hours (6 days), about 54 hours to about 120hours (5 days), about 54 hours to about 96 hours (4 days), about 54hours to about 72 hours (3 days), about 54 hours to about 66 hours,about 54 hours to about 60 hours, about 60 hours to about 144 hours (6days), about 60 hours to about 120 hours (5 days), about 60 hours toabout 96 hours (4 days), about 60 hours to about 72 hours (3 days),about 60 hours to about 66 hours, about 66 hours to about 144 hours (6days), about 66 hours to about 120 hours (5 days), about 66 hours toabout 96 hours (4 days), about 66 hours to about 72 hours (3 days),about 72 hours (3 days) to about 144 hours (6 days), about 72 hours (3days) to about 120 hours (5 days), about 72 hours (3 days) to about 96hours (4 days), about 96 hours (4 days) to about 144 hours (6 days),about 96 hours (4 days) to about 120 hours (5 days), or about 120 hours(5 days) to about 144 hours (6 days).

Additionally or alternatively, the solution formed in the method can beaged at temperature of at least about 10° C., at least about 20° C., atleast about 30° C., at least about 40° C., at least about 50° C., atleast about 60° C., at least about 70° C., at least about 80° C., atleast about 90° C., at least about 100° C., at least about 110° C., atleast about 120° C. at least about 130° C., at least about 140° C., atleast about 150° C., at least about 175° C., at least about 200° C., atleast about 250° C., or about 300° C.

Additionally or alternatively, the solution formed in the method can beaged at temperature of about 10° C. to about 300° C., about 10° C. toabout 250° C., about 10° C. to about 200° C., about 10° C. to about 175°C., about 10° C. to about 150° C., about 10° C. to about 140° C., about10° C. to about 130° C., about 10° C. to about 120° C., about 10° C. toabout 110° C., about 10° C. to about 100° C., about 10° C. to about 90°C., about 10° C. to about 80° C., about 10° C. to about 70° C., about10° C. to about 60° C., about 10° C. to about 50° C., about 20° C. toabout 300° C., about 20° C. to about 250° C., about 20° C. to about 200°C., about 20° C. to about 175° C., about 20° C. to about 150° C., about20° C. to about 140° C., about 20° C. to about 130° C., about 20° C. toabout 120° C., about 20° C. to about 110° C., about 20° C. to about 100°C., about 20° C. to about 90° C., about 20° C. to about 80° C., about20° C. to about 70° C., about 20° C. to about 60° C., about 20° C. toabout 50° C., about 30° C. to about 300° C., about 30° C. to about 250°C., about 30° C. to about 200° C., about 30° C. to about 175° C., about30° C. to about 150° C., about 30° C. to about 140° C., about 30° C. toabout 130° C., about 30° C. to about 120° C., about 30° C. to about 110°C., about 30° C. to about 100° C., about 30° C. to about 90° C., about30° C. to about 80° C., about 30° C. to about 70° C., about 30° C. toabout 60° C., about 30° C. to about 50° C., about 50° C. to about 300°C., about 50° C. to about 250° C., about 50° C. to about 200° C., about50° C. to about 175° C., about 50° C. to about 150° C., about 50° C. toabout 140° C., about 50° C. to about 130° C., about 50° C. to about 120°C., about 50° C. to about 110° C., about 50° C. to about 100° C., about50° C. to about 90° C., about 50° C. to about 80° C., about 50° C. toabout 70° C., about 50° C. to about 60° C., about 70° C. to about 300°C., about 70° C. to about 250° C., about 70° C. to about 200° C., about70° C. to about 175° C., about 70° C. to about 150° C., about 70° C. toabout 140° C., about 70° C. to about 130° C., about 70° C. to about 120°C., about 70° C. to about 110° C., about 70° C. to about 100° C., about70° C. to about 90° C., about 70° C. to about 80° C., about 80° C. toabout 300° C., about 80° C. to about 250° C., about 80° C. to about 200°C., about 80° C. to about 175° C., about 80° C. to about 150° C., about80° C. to about 140° C., about 80° C. to about 130° C., about 80° C. toabout 120° C., about 80° C. to about 110° C., about 80° C. to about 100°C., about 80° C. to about 90° C., about 90° C. to about 300° C., about90° C. to about 250° C., about 90° C. to about 200° C., about 90° C. toabout 175° C., about 90° C. to about 150° C., about 90° C. to about 140°C., about 90° C. to about 130° C., about 90° C. to about 120° C., about90° C. to about 110° C., about 90° C. to about 100° C., about 100° C. toabout 300° C., about 100° C. to about 250° C., about 100° C. to about200° C., about 100° C. to about 175° C., about 100° C. to about 150° C.,about 100° C. to about 140° C., about 100° C. to about 130° C., about100° C. to about 120° C., about 100° C. to about 110° C., about 110° C.to about 300° C., about 110° C. to about 250° C., about 110° C. to about200° C., about 110° C. to about 175° C., about 110° C. to about 150° C.,about 110° C. to about 140° C., about 110° C. to about 130° C., about110° C. to about 120° C., about 120° C. to about 300° C., about 120° C.to about 250° C., about 120° C. to about 200° C., about 120° C. to about175° C., about 120° C. to about 150° C., about 120° C. to about 140° C.,about 120° C. to about 130° C., about 130° C. to about 300° C., about130° C. to about 250° C., about 130° C. to about 200° C., about 130° C.to about 175° C., about 130° C. to about 150° C., or about 130° C. toabout 140° C.

III.I. Drying the Pre-Product

The methods described herein comprise drying the pre-product (e.g., agel) to produce an organosilica material.

In some embodiments, the pre-product (e.g., a gel) formed in the methodcan be dried at a temperature of greater than or equal to about 50° C.,greater than or equal to about 70° C., greater than or equal to about80° C., greater than or equal to about 100° C., greater than or equal toabout 110° C., greater than or equal to about 120° C., greater than orequal to about 150° C., greater than or equal to about 200° C., greaterthan or equal to about 250° C., greater than or equal to about 300° C.,greater than or equal to about 350° C., greater than or equal to about400° C., greater than or equal to about 450° C., greater than or equalto about 500° C., greater than or equal to about 550° C., or greaterthan or equal to about 600° C.

Additionally or alternatively, the pre-product (e.g., a gel) formed inthe method can be dried at temperature of about 50° C. to about 600° C.,about 50° C. to about 550° C., about 50° C. to about 500° C., about 50°C. to about 450° C., about 50° C. to about 400° C., about 50° C. toabout 350° C., about 50° C. to about 300° C., about 50° C. to about 250°C., about 50° C. to about 200° C., about 50° C. to about 150° C., about50° C. to about 120° C., about 50° C. to about 110° C., about 50° C. toabout 100° C., about 50° C. to about 80° C., about 50° C. to about 70°C., about 70° C. to about 600° C., about 70° C. to about 550° C., about70° C. to about 500° C., about 70° C. to about 450° C., about 70° C. toabout 400° C., about 70° C. to about 350° C., about 70° C. to about 300°C., about 70° C. to about 250° C., about 70° C. to about 200° C., about70° C. to about 150° C., about 70° C. to about 120° C., about 70° C. toabout 110° C., about 70° C. to about 100° C., about 70° C. to about 80°C., about 80° C. to about 600° C., about 70° C. to about 550° C., about80° C. to about 500° C., about 80° C. to about 450° C., about 80° C. toabout 400° C., about 80° C. to about 350° C., about 80° C. to about 300°C., about 80° C. to about 250° C., about 80° C. to about 200° C., about80° C. to about 150° C., about 80° C. to about 120° C., about 80° C. toabout 110° C., or about 80° C. to about 100° C.

In a particular embodiment, the pre-product (e.g., a gel) formed in themethod can be dried at temperature from about 70° C. to about 200° C.

Additionally or alternatively, the pre-product (e.g., a gel) formed inthe method can be dried in a N₂ and/or air atmosphere.

III.K. Optional Further Steps

In some embodiments, the method can further comprise calcining theorganosilica material to obtain a silica material. The calcining can beperformed in air or an inert gas, such as nitrogen or air enriched innitrogen. Calcining can take place at a temperature of at least about300° C., at least about 350° C., at least about 400° C., at least about450° C., at least about 500° C., at least about 550° C., at least about600° C., or at least about 650° C., for example at least about 400° C.Additionally or alternatively, calcining can be performed at atemperature of about 300° C. to about 650° C., about 300° C. to about600° C., about 300° C. to about 550° C., about 300° C. to about 400° C.,about 300° C. to about 450° C., about 300° C. to about 400° C., about300° C. to about 350° C., about 350° C. to about 650° C., about 350° C.to about 600° C., about 350° C. to about 550° C., about 350° C. to about400° C., about 350° C. to about 450° C., about 350° C. to about 400° C.,about 400° C. to about 650° C., about 400° C. to about 600° C., about400° C. to about 550° C., about 400° C. to about 500° C., about 400° C.to about 450° C., about 450° C. to about 650° C., about 450° C. to about600° C., about 450° C. to about 550° C., about 450° C. to about 500° C.,about 500° C. to about 650° C., about 500° C. to about 600° C., about500° C. to about 550° C., about 550° C. to about 650° C., about 550° C.to about 600° C. or about 600° C. to about 650° C.

IV. ORGANOSILICA MATERIAL PRODUCT-BY-PROCESS

Organosilica materials can be made from the methods described herein. Inanother particular embodiment, organosilica materials made from anaqueous mixture as described herein that contains essentially nostructure directing agent or porogen as described herein, wherein theorganosilica material may be:

(i) a copolymer of:

-   -   (a) at least one independent unit of Formula (I) as described        herein:    -   (b) at least one independent unit of Formula (II) as described        herein and/or at least one independent unit of Formula (III) as        described herein; and    -   (c) optionally, at least one independent unit of Formula (IV) as        described herein, Formula (V) as described herein, and/or at        least one unit of Formula (VI) as described herein.

The organosilica materials made from the methods described herein mayexhibit an XRD pattern as described herein, particularly with only onepeak between about 0.5 and about 3 degrees 2θ. Additionally oralternatively, the organosilica materials made from the methodsdescribed herein can exhibit substantially no peaks in the range ofabout 0.5 to about 10 degrees 2θ, about 0.5 to about 12 degrees 2θrange, about 0.5 to about 15 degrees 2θ, about 0.5 to about 20 degrees2θ, about 0.5 to about 30 degrees 2θ, about 0.5 to about 40 degrees 2θ,about 0.5 to about 50 degrees 2θ, about 0.5 to about 60 degrees 2θ,about 0.5 to about 70 degrees 2θ, about 2 to about 10 degrees 2θ, about2 to about 12 degrees 2θ range, about 2 to about 15 degrees 2θ, about 2to about 20 degrees 2θ, about 2 to about 30 degrees 2θ, about 2 to about40 degrees 2θ, about 2 to about 50 degrees 2θ, about 2 to about 60degrees 2θ, about 2 to about 70 degrees 2θ, about 3 to about 10 degrees2θ, about 3 to about 12 degrees 2θ range, about 3 to about 15 degrees2θ, about 3 to about 20 degrees 2θ, about 3 to about 30 degrees 2θ,about 3 to about 40 degrees 2θ, about 3 to about 50 degrees 2θ, about 3to about 60 degrees 2θ, or about 3 to about 70 degrees 2θ.

Additionally or alternatively, the organosilica materials may have anaverage pore diameter as described herein, particularly, between about2.0 nm and about 25.0 nm.

V. USES OF THE ORGANOSILICA MATERIALS

The organosilica materials described herein find uses in several areas.

In certain embodiments, the organosilica material described herein canbe used as adsorbents or support matrices for separation and/orcatalysis processes.

V.A. Gas Separation Processes

In some cases, the organosilica materials can be used in a gasseparation process as provided herein. In various aspects, a gasseparation process is provided herein. The gas separation process cancomprise contacting a gas mixture containing at least one contaminantwith the organosilica material described herein as prepared according tothe methods described herein.

In various embodiments, the gas separation process can be achieved byswing adsorption processes, such as pressure swing adsorption (PSA) andtemperature swing adsorption (TSA). All swing adsorption processestypically have an adsorption step in which a feed mixture (typically inthe gas phase) is flowed over an adsorbent to preferentially adsorb amore readily adsorbed component relative to a less readily adsorbedcomponent. A component may be more readily adsorbed because of kineticor equilibrium properties of the adsorbent. The adsorbent (e.g., theorganosilica material described herein) can typically be contained in acontactor that is part of the swing adsorption unit. The contactor cantypically contain an engineered structured adsorbent bed or aparticulate adsorbent bed. The bed can contain the adsorbent (e.g., theorganosilica material described herein) and other materials such asother adsorbents, mesopore filling materials, and/or inert materialsused to mitigated temperature excursions from the heat of adsorption anddesorption. Other components in the swing adsorption unit can include,but are not necessarily limited to, valves, piping, tanks, and othercontactors. Swing adsorption processes are described in detail in U.S.Pat. Nos. 8,784,533; 8,784,534; 8,858,683; and 8,784,535, each of whichare incorporated herein by reference. Examples of processes that can beused herein either separately or in combination are PSA, TSA, pressuretemperature swing adsorption (PTSA), partial purge displacement swingadsorption (PPSA), PPTSA, rapid cycle PSA (RCPSA), RCTSA, RCPPSA andRCPTSA.

PSA processes rely on the fact that gases under pressure tend to beadsorbed within the pore structure of the adsorbent materials (e.g., theorganosilica material described herein). Typically, the higher thepressure, the greater the amount of targeted gas component that will beadsorbed. When the pressure is reduced, the adsorbed targeted componentis typically released, or desorbed. PSA processes can be used toseparate gases of a gas mixture, because different gases tend to fillthe pores or free volume of the adsorbent to different extents due toeither the equilibrium or kinetic properties of the adsorbent. In manyimportant applications, to be described as “equilibrium-controlled”processes, the adsorptive selectivity is primarily based upondifferential equilibrium uptake of the first and second components. Inanother important class of applications, to be described as“kinetic-controlled” processes, the adsorptive selectivity is primarilybased upon the differential rates of uptake of the first and secondcomponents.

If a gas mixture, such as natural gas, is passed under pressure througha vessel containing a polymeric or microporous adsorbent that is moreselective towards carbon dioxide than it is for methane, at least aportion of the carbon dioxide can be selectively adsorbed by theadsorbent, and the gas exiting the vessel can be enriched in methane.When the adsorbent (e.g., the organosilica material described herein)reaches the end of its capacity to adsorb carbon dioxide, it can beregenerated by reducing the pressure, thereby releasing the adsorbedcarbon dioxide. The adsorbent can then typically purged andrepressurized and ready for another adsorption cycle.

TSA processes also rely on the fact that gases under pressure tend to beadsorbed within the pore structure of the adsorbent materials. When thetemperature of the adsorbent (e.g., the organosilica material describedherein) is increased, the adsorbed gas is typically released, ordesorbed. By cyclically swinging the temperature of adsorbent beds, TSAprocesses can be used to separate gases in a mixture when used with anadsorbent selective for one or more of the components in a gas mixture.Partial pressure purge displacement (PPSA) swing adsorption processesregenerate the adsorbent with a purge. Rapid cycle (RC) swing adsorptionprocesses complete the adsorption step of a swing adsorption process ina short amount of time. For kinetically selective adsorbents, it can bepreferable to use a rapid cycle swing adsorption process. If the cycletime becomes too long, the kinetic selectivity can be lost. These swingadsorption protocols can be performed separately or in combinations.Examples of processes that can be used herein either separately or incombination are PSA, TSA, pressure temperature swing adsorption (PTSA),partial purge displacement swing adsorption (PPSA), PPTSA, rapid cyclePSA (RCPSA), RCTSA, vacuum pressure swing adsorption (VPSA), RCPPSA andRCPTSA.

In PSA processes, a feed gas mixture containing the first and second gascomponents is separated by cyclic variations of pressure coordinatedwith cyclic reversals of flow direction in a flow path contacting afixed bed of the adsorbent material in an adsorber vessel. In the caseof TSA or PPSA processes, cyclic variations of temperature and/orpartial pressure of the gas components may be coordinated with gas flowthrough a flow path to perform a separation. The process in any specificPSA application operates at a cyclic frequency characterized by itsperiod, and over a pressure envelope between a first relatively higherpressure and a second relatively lower pressure. Separation in PSA isachieved by coordinating the pressure variations with the flow patternwithin the flow path, so that the gas mixture in the flow path isenriched in the second component (owing to preferential adsorptiveuptake of the first component in the adsorbent material) when flowing ina first direction in the flow path, while the gas mixture is enriched inthe first component (which has been desorbed by the adsorbent material)when flowing in the opposite direction in the flow path. In order toachieve separation performance objectives (i.e. product gas purity,recovery and productivity), process parameters and operating conditionsshould be designed to achieve a sufficiently high adsorptive selectivityof the first and second components over the adsorbent material, at thecyclic frequency and within the pressure envelope.

Swing adsorption processes can be applied to remove a variety of targetgases, also referred to as “contaminant gas” from a wide variety of gasmixtures. Typically, in binary separation systems, the “light component”as utilized herein is taken to be the species or molecular component(s)not preferentially taken up by the adsorbent in the adsorption step ofthe process. Conversely in such binary systems, the “heavy component” asutilized herein is typically taken to be the species or molecularcomponent(s) preferentially taken up by the adsorbent in the adsorptionstep of the process. However, in binary separation systems where thecomponent(s) that is(are) preferentially adsorbed has(have) a lowermolecular weight than the component(s) that is(are) not preferentiallyadsorbed, those descriptions may not necessarily correlate as disclosedabove.

An example of gas mixture that can be separated in the methods describedherein is a gas mixture comprising CH₄, such as a natural gas stream. Agas mixture comprising CH₄ can contain significant levels ofcontaminants such as H₂O, H₂S, CO₂, N₂, mercaptans, and/or heavyhydrocarbons. Additionally or alternatively, the gas mixture cancomprise NO_(x) and/or SO_(x) species as contaminants, such as a wastegas stream, a flue gas stream and a wet gas stream. As used herein, theterms “NO_(x),” and “NO_(x)” species refers to the various oxides ofnitrogen that may be present in waste gas, such as waste gas fromcombustion processes. The terms refer to all of the various oxides ofnitrogen including, but not limited to, nitric oxide (NO), nitrogendioxide (NO₂), nitrogen peroxide (N₂O), nitrogen pentoxide (N₂O₅), andmixtures thereof. As used herein, the terms “SO_(x),” and “SO_(x)species,” refers to the various oxides of sulfur that may be present inwaste gas, such as waste gas from combustion processes. The terms referto all of the various oxides of sulfur including, but not limited to,SO, SO₂, SO₃, SO₄, S₇O₂ and S₆O₂. Thus, examples of contaminantsinclude, but are not limited to H₂O, H₂S, CO₂, N₂, mercaptans, heavyhydrocarbons, NO_(x) and/or SO_(x) species. In particular, the gasmixture may comprise CH₄ and the at least one contaminant is CO₂ and/orH₂S.

In various aspects, a process for selectively separating a contaminantfrom a feed gas mixture is provided herein. The process may comprise: a)contacting the feed gas mixture under sorption conditions withorganosilica material described herein; b) adsorbing the contaminantinto/onto the organosilica material described herein; c) subjecting theorganosilica material described herein to desorption conditions by whichat least a portion of the sorbed contaminant is desorbed; and d)retrieving a contaminant-rich product stream that has a higher mol % ofcontaminant than the feed gas mixture. The feed gas mixture may be anyof the gas mixtures described above. Particularly, the feed gas mixturemay comprise CH₄. The contaminant may be any of the contaminantsdescribed above, e.g., CO₂, H₂S, etc.

It may be desirable to operate with a multiplicity of structureadsorbent beds, with several coupled in a heating/cooling operation andothers involved in adsorption (and/or desorption). In such an operation,the adsorbent bed can be substantially cooled by a circulating heattransfer medium before it is switched into service for adsorption. Oneadvantage of such an operation can be that the thermal energy used toswing the bed is retained in the heat transfer medium. If adsorptionwere to proceed simultaneously with cooling, then a substantial part ofthe heat in the bed could be lost to the adsorbate-free feed, and ahigher heat load could be needed to restore the high temperature of theheat transfer medium.

Adsorptive kinetic separation (AKS) processes, as described above, areuseful for development and production of hydrocarbons, such as gas andoil processing. Particularly, as described in U.S. Patent ApplicationPublication No. 2013/032716, which is herein incorporated by referencein its entirety, the AKS processes described herein can use one or morekinetic swing adsorption process, such as pressure swing adsorption(PSA), thermal swing adsorption (TSA), calcination, and partial pressureswing or displacement purge adsorption (PPSA), including combinations ofthese processes; each swing adsorption process may be utilized withrapid cycles, such as using one or more rapid cycle pressure swingadsorption (RC-PSA) units, with one or more rapid cycle temperatureswing adsorption (RC-TSA) units or with one or more rapid cycle partialpressure swing adsorption (RC-PPSA) units; exemplary kinetic swingadsorption processes are described in U.S. Pat. Nos. 7,959,720;8,545,602; 8,529,663; 8,444,750; and 8,529,662 and U.S. ProvisionalApplication Nos. 61/448,121; 61/447,848; 61/447,869; and 61/447,877,which are each herein incorporated by reference in its entirety. Theprovided processes, can be useful for rapid, large scale, efficientseparation of a variety of target gases from gas mixtures.

The provided processes and apparatuses may be used to prepare naturalgas products by removing contaminants. The provided processes andapparatuses can be useful for preparing gaseous feed streams for use inutilities, including separation applications such as dew point control,sweetening/detoxification, corrosion protection/control, dehydration,heating value, conditioning, and purification. Examples of utilitiesthat utilize one or more separation applications can include generationof fuel gas, seal gas, non-potable water, blanket gas, instrument andcontrol gas, refrigerant, inert gas, and hydrocarbon recovery. Exemplary“not to exceed” product (or “target”) acid gas removal specificationscan include: (a) 2 vol % CO₂, 4 ppm H₂S; (b) 50 ppm CO₂, 4 ppm H₂S; or(c) 1.5 vol % CO₂, 2 ppm H₂S.

The provided processes and apparatuses may also be used to remove acidgas from hydrocarbon streams. Acid gas removal technology becomesincreasingly important as remaining gas reserves exhibit higherconcentrations of acid (sour) gas resources. Hydrocarbon feed streamscan vary widely in amount of acid gas, such as from several parts permillion to 90 vol %. Non-limiting examples of acid gas concentrationsfrom exemplary gas reserves can include concentrations of at least: (a)1 vol % H₂S, 5 vol % CO₂; (b) 1 vol % H₂S, 15 vol % CO₂; (c) 1 vol %H₂S, 60 vol % CO₂; (d) 15 vol % H₂S, 15 vol % CO₂; or (e) 15 vol % H₂S,30 vol % CO₂.

One or more of the following may be utilized with the processes andapparatuses provided herein, to prepare a desirable product stream,while maintaining relatively high hydrocarbon recovery:

(a) removing acid gas with RC-TSA using advanced cycles and purges asdescribed in U.S. Provisional Application No. 61/447,854, filed Mar. 1,2011, as well as the U.S. Pat. No. 8,784,533, which are togetherincorporated by reference herein in their entirety;

(b) using a mesopore filler to reduce the amount of trapped methane inthe adsorbent bed and increase the overall hydrocarbon recovery, asdescribed in U.S. Pat. Nos. 7,959,720; 8,444,750; and 8,529,663, each ofwhich is herein incorporated by reference in its entirety;

(c) depressurizing one or more RC-TSA units in multiple steps tointermediate pressures so that the acid gas exhaust can be captured at ahigher average pressure, thereby decreasing the compression required foracid gas injection; pressure levels for the intermediatedepressurization steps may be matched to the interstage pressures of theacid gas compressor to optimize the overall compression system;

(d) using exhaust or recycle streams to minimize processing andhydrocarbon losses, such as using exhaust streams from one or moreRC-TSA units as fuel gas instead of re-injecting or venting;

(e) using multiple adsorbent particles in a single bed to remove traceamounts of first contaminants, such as H₂S, before removal of a secondcontaminant, such as CO₂; such segmented beds may provide rigorous acidgas removal down to ppm levels with RC-TSA units with minimal purge flowrates;

(f) using feed compression before one or more RC-TSA units to achieve adesired product purity;

(g) contemporaneous removal of non-acid gas contaminants such asmercaptans, COS, and BTEX; selection processes and materials toaccomplish the same;

(h) selecting a cycle time and cycle steps based on adsorbent materialkinetics; and

(i) using a process and apparatus that uses, among other equipment, twoRC-TSA units in series, wherein the first RC-TSA unit cleans a feedstream down to a desired product purity and the second RC-TSA unitcleans the exhaust from the first unit to capture methane and maintainhigh hydrocarbon recovery; use of this series design may reduce the needfor a mesopore filler.

The processes, apparatuses, and systems provided herein can be useful inlarge gas treating facilities, such as facilities that process more thanfive million standard cubic feet per day (MSCFD) of natural gas, forexample more than 15 MSCFD, more than 25 MSCFD, more than 50 MSCFD, morethan 100 MSCFD, more than 500 MSCFD, more than one billion standardcubic feet per day (BSCFD), or more than two BSCFD.

V.B. Aromatic Hydrogenation Process

The organosilica materials made according to the methods describedherein can be used as support materials in hydrogenation catalysts. Inparticular, the hydrogenation catalyst can comprise the organosilicamaterials as a support material where the organosilica material has atleast one catalyst metal incorporated on the pore surface. The at leastone catalyst metal may be a Group 8 metal, a Group 9 metal, a Group 10metal, e.g., Pt, Pd, Ir, Rh, Ru or a combination thereof. Thehydrogenation catalyst can further comprise a binder such as, but notlimited to, active and inactive materials, inorganic materials, clays,ceramics, activated carbon, alumina, silica, silica-alumina, titania,zirconia, niobium oxide, tantalum oxide, or a combination thereof,particularly, silica-alumina, alumina, titania, or zirconia. Thesehydrogenation catalysts can be used for both hydrogenation and aromaticsaturation of a feedstream.

In various embodiments, the hydrogenation process can be achieved bycontacting a hydrocarbon feedstream comprising aromatics with ahydrogenation catalyst described herein in the presence of ahydrogen-containing treat gas in a first reaction stage operated undereffective aromatics hydrogenation conditions to produce a reactionproduct with reduced aromatics content.

Hydrogen-containing treat gasses suitable for use in a hydrogenationprocess can be comprised of substantially pure hydrogen or can bemixtures of other components typically found in refinery hydrogenstreams. It is preferred that the hydrogen-containing treat gas streamcontains little, more preferably no, hydrogen sulfide. Thehydrogen-containing treat gas purity should be at least about 50% byvolume hydrogen, preferably at least about 75% by volume hydrogen, andmore preferably at least about 90% by volume hydrogen for best results.It is most preferred that the hydrogen-containing stream besubstantially pure hydrogen.

Feedstreams suitable for hydrogenation by the hydrogenation catalystdescribed herein include any conventional hydrocarbon feedstreams wherehydrogenation or aromatic saturation is desirable. Typically, an inputfeed for an aromatic saturation process can be generated as a product orside-product from a previous type of hydroprocessing, such ashydrocracking for fuels or lubricant base stock production. A wide rangeof petroleum and chemical feedstocks can be hydroprocessed. Suchfeedstreams can include hydrocarbon fluids, diesel, kerosene,lubricating oil feedstreams, heavy coker gasoil (HKGO), de-asphalted oil(DAO), FCC main column bottom (MCB), steam cracker tar. Such feedstreamscan also include other distillate feedstreams such as light to heavydistillates including raw virgin distillates, wax-containing feedstreamssuch as feeds derived from crude oils, shale oils and tar sands.Synthetic feeds such as those derived from the Fischer-Tropsch processcan also be aromatically saturated using the hydrogenation catalystdescribed herein. Typical wax-containing feedstocks for the preparationof lubricating base oils have initial boiling points of about 315° C. orhigher, and include feeds such as whole and reduced petroleum crudes,hydrocrackates, raffinates, hydrotreated oils, gas oils (such asatmospheric gas oils, vacuum gas oils, and coker gas oils), atmosphericand vacuum residues, deasphalted oils/residua (e.g., propane deasphaltedresidua, brightstock, cycle oil), dewaxed oils, slack waxes andFischer-Tropsch wax, and mixtures of these materials. Such feeds may bederived from distillation towers (atmospheric and vacuum),hydrocrackers, hydrotreaters and solvent extraction units, and may havewax contents of up to 50% or more. Preferred lubricating oil boilingrange feedstreams include feedstreams which boil in the range of650-1100° F. Diesel boiling range feedstreams include feedstreams whichboil in the range of 480-660° F. Kerosene boiling range feedstreamsinclude feedstreams which boil in the range of 350-617° F.

Hydrocarbon feedstreams suitable for use herein also contain aromaticsand nitrogen- and sulfur-contaminants. Feedstreams containing up to 0.2wt. % of nitrogen, based on the feedstream, up to 3.0 wt. % of sulfur,and up to 50 wt. % aromatics can be used in the present process Invarious embodiments, the sulfur content of the feedstreams can be belowabout 500 wppm, or below about 300 wppm, or below about 200 wppm, orbelow about 100 wppm, or below about 50 wppm, or below about 15 wppm.The pressure used during an aromatic hydrogenation process can bemodified based on the expected sulfur content in a feedstream. Feedshaving a high wax content typically have high viscosity indexes of up to200 or more. Sulfur and nitrogen contents may be measured by standardASTM methods D2622 (sulfur), and D5453 and/or D4629 (nitrogen),respectively.

Effective hydrogenation conditions may be considered to be thoseconditions under which at least a portion of the aromatics present inthe hydrocarbon feedstream are saturated, preferably at least about 50wt. % of the aromatics are saturated, more preferably greater than about75 wt. %. Effective hydrogenation conditions can include temperatures offrom 150° C. to 400° C., a hydrogen partial pressure of from 740 to20786 kPa (100 to 3000 psig), a space velocity of from 0.1 to 10 liquidhourly space velocity (LHSV), and a hydrogen to feed ratio of from 89 to1780 m³/m³ (500 to 10000 scf/B).

Additionally or alternatively, effective hydrogenation conditions may beconditions effective at removing at least a portion of the nitrogen andorganically bound sulfur contaminants and hydrogenating at least aportion of said aromatics, thus producing at least a liquid lube boilingrange product having a lower concentration of aromatics and nitrogen andorganically bound sulfur contaminants than the lube boiling rangefeedstream.

Additionally or alternatively, effective hydrogenation conditions may beconditions effective at removing at least a portion of the nitrogen andorganically bound sulfur contaminants and hydrogenating at least aportion of said aromatics, thus producing at least a liquid dieselboiling range product having a lower concentration of aromatics andnitrogen and organically bound sulfur contaminants than the dieselboiling range feedstream.

As stated above, in some instances, the hydrocarbon feedstream (e.g.,lube oil boiling range) may be hydrotreated to reduce the sulfurcontaminants to below about 500 wppm, particularly below about 300 wppm,particularly below about 200 wppm or particularly below about 100 wppm.In such an embodiment, the process may comprise at least two reactionstages, the first reaction state containing a hydrotreating catalystoperated under effective hydrotreating conditions, and the secondcontaining a hydrogenation catalyst has described herein operated undereffective hydrogenation conditions as described above. Therefore, insuch an embodiment, the hydrocarbon feedstream can be first contactedwith a hydrotreating catalyst in the presence of a hydrogen-containingtreat gas in a first reaction stage operated under effectivehydrotreating conditions in order to reduce the sulfur content of thefeedstream to within the above-described range. Thus, the term“hydrotreating” as used herein refers to processes wherein ahydrogen-containing treat gas is used in the presence of a suitablecatalyst that is active for the removal of heteroatoms, such as sulfur,and nitrogen. Suitable hydrotreating catalysts for use in the presentinvention are any conventional hydrotreating catalyst and includes thosewhich are comprised of at least one Group 8 metal, preferably Fe, Co andNi, more preferably Co and/or Ni, and most preferably Ni; and at leastone Group 6 metal, preferably Mo and W, more preferably Mo, on a highsurface area support material, preferably alumina. Additionally oralternatively, more than one type of hydrotreating catalyst can be usedin the same reaction vessel. The Group 8 metal may typically be presentin an amount ranging from about 2 to 20 wt. %, preferably from about 4to 12 wt. %. The Group 6 metal can typically be present in an amountranging from about 5 to 50 wt. %, preferably from about 10 to 40 wt. %,and more preferably from about 20 to 30 wt. %. All metals weightpercents are “on support” as described above.

Effective hydrotreating conditions may be considered to be thoseconditions that can effectively reduce the sulfur content of thefeedstream (e.g., lube oil boiling range) to within the above-describedranges. Typical effective hydrotreating conditions can includetemperatures ranging from about 150° C. to about 425° C., preferablyabout 200° C. to about 370° C., more preferably about 230° C. to about350° C. Typical weight hourly space velocities (“WHSV”) may range fromabout 0.1 to about 20 hr⁻¹, preferably from about 0.5 to about 5 hr⁻¹.Any effective pressure can be utilized, and pressures can typicallyrange from about 4 to about 70 atmospheres (405 to 7093 kPa), preferably10 to 40 atmospheres (1013 to 4053 kPa). In a particular embodiment,said effective hydrotreating conditions may be conditions effective atremoving at least a portion of said organically bound sulfurcontaminants and hydrogenating at least a portion of said aromatics,thus producing at least a reaction product (e.g., liquid lube oilboiling range product) having a lower concentration of aromatics andorganically bound sulfur contaminants than the lube oil boiling rangefeedstream.

The contacting of the hydrocarbon feedstream with the hydrotreatingcatalyst may produce a reaction product comprising at least a vaporproduct and a liquid product. The vapor product may typically comprisegaseous reaction products, such as H₂S, and the liquid reaction productmay typically comprise a liquid hydrocarbon having a reduced level ofnitrogen and sulfur contaminants. The total reaction product can bepassed directly into the second reaction stage, but it may be preferredthat the gaseous and liquid reaction products be separated, and theliquid reaction product conducted to the second reaction stage. Thus, inone embodiment, the vapor product and the liquid product may beseparated, and the liquid product may be conducted to the secondreaction stage. The method of separating the vapor product from theliquid product can be accomplished by any means known to be effective atseparating gaseous and liquid reaction products. For example, astripping tower or reaction zone can be used to separate the vaporproduct from the liquid product (e.g., liquid lube oil boiling rangeproduct). The liquid product thus conducted to the second reaction stagecan have a sulfur concentration within the range of about 500 wppm,particularly below about 300 wppm, or particularly below about 200 wppmor particularly below about 100 wppm.

In still other embodiments, the hydrogenation catalysts described hereincan be used in integrated hydroprocessing methods. In addition to thehydrofinishing and/or aromatic hydrogenation/saturation processesinvolving the hydrogenation catalyst described herein, an integratedhydroprocessing method can also include various combinations ofhydrotreating, hydrocracking, catalytic dewaxing (such ashydrodewaxing), and/or solvent dewaxing. The scheme of hydrotreatingfollowed by hydrofinishing described above represents one type ofintegrated process flow. Another integrated processing example is tohave a dewaxing step, either catalytic dewaxing or solvent dewaxing,followed by hydroprocessing with the hydrogenation catalysts describedherein. Still another example is a process scheme involvinghydrotreating, dewaxing (catalytic or solvent), and then hydroprocessingwith the hydrogenation catalysts described herein. Yet another exampleis hydroprocessing with the hydrogenation catalysts described hereinfollowed by dewaxing (catalytic or solvent). Alternatively, multiplehydrofinishing and/or aromatic hydrogenation steps can be employed withhydrotreatment, hydrocracking, or dewaxing steps. An example of such aprocess flow is hydrofinishing, dewaxing (catalytic or solvent), andthen hydrofinishing again, where at least one of the hydrofinishingsteps may use a hydrogenation catalysts described herein. For processesinvolving catalytic dewaxing, effective catalytic dewaxing conditionscan include temperatures of from 150° C. to 400° C., preferably 250° C.to 350° C., pressures of from 791 to 20786 kPa (100 to 3000 psig),preferably 1480 to 17338 kPa (200 to 2500 psig), liquid hourly spacevelocities of from 0.1 to 10 hr⁻¹, preferably 0.1 to 5 hr⁻¹ and hydrogentreat gas rates from 45 to 1780 m³/m³ (250 to 10000 scf/B), preferably89 to 890 m³/m³ (500 to 5000 scf/B). Any suitable dewaxing catalyst maybe used.

In embodiments where the product of an aromatic saturation process willbe a lubricant base oil, the input feed should also have suitablelubricant base oil properties. For example, an input feed intended foruse as a Group I or Group II base oil can have a viscosity index (VI) ofat least about 80, preferably at least about 90 or at least about 95. Aninput feed intended for use as a Group I+ base oil can have a VI of atleast about 100, while an input feed intended for use as a Group II+base oil can have a VI of at least 110. The viscosity of the input feedcan be at least 2 cSt at 100° C., or at least 4 cSt at 100° C., or atleast 6 cSt at 100° C.

VI. FURTHER EMBODIMENTS

The invention can additionally or alternately include one or more of thefollowing embodiments.

Embodiment 1

An organosilica material, which is a polymer of at least one independentmonomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² eachindependently represent a hydrogen atom, a C₁-C₄ alkyl group or a bondto a silicon atom of another monomer and at least one other monomerselected from the group consisting of:

-   -   (i) an independent unit of Formula Z³OZ⁴Z⁵Z⁶ (II), wherein each        Z³ represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to        a silicon atom of another monomer; and Z⁴, Z⁵ and Z⁶ are each        independently selected from the group consisting of a hydroxyl        group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a        nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing        heteroaralkyl group, a nitrogen-containing optionally        substituted heterocycloalkyl group, and an oxygen atom bonded to        a silicon atom of another monomer;    -   (ii) an independent unit of Formula Z⁷Z⁸Z⁹Si—R¹—SiZ⁷Z⁸Z⁹ (III),        wherein each Z⁷ independently represents a hydroxyl group, a        C₁-C₄ alkoxy group or an oxygen bonded to a silicon atom of        another comonomer; each Z8 and Z9 independently represent a        hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an        oxygen bonded to a silicon atom of another monomer; and each R¹        represents a nitrogen-containing C₂-C₁₀ alkylene group; and    -   (iii) a combination thereof.

Embodiment 2

The organosilica material of embodiment 1, wherein Z¹ and Z² eachindependently represent a hydrogen atom, a C₁-C₂ alkyl group or a bondto a silicon atom of another monomer.

Embodiment 3

The organosilica material of embodiment 1 or 2, wherein Z¹ and Z² eachindependently represent a hydrogen atom, ethoxy or a bond to a siliconatom of another monomer.

Embodiment 4

The organosilica material of any one of the previous embodiments,wherein at least one independent unit of Formula (II) is present,wherein each Z³ represents a hydrogen atom, a C₁-C₂ alkyl group or abond to a silicon atom of another comonomer; and Z⁴, Z⁵ and Z⁶ are eachindependently selected from the group consisting of a hydroxyl group, aC₁-C₂ alkyl group, C₁-C₂ alkoxy group, a nitrogen-containing C₄-C₁₀alkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or anitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkylgroup.

Embodiment 5

The organosilica material of embodiment 4, wherein each Z³ represents ahydrogen atom, methyl, ethyl, or a bond to a silicon atom of anothercomonomer; and Z⁴, Z⁵ and Z⁶ are each independently selected from thegroup consisting of a hydroxyl group, methoxy, ethoxy

and an oxygen bonded to a silicon atom of another monomer.

Embodiment 6

The organosilica material of any one of the previous embodiments,wherein at least one independent unit of Formula (III) is present,wherein each Z⁷ represents a hydroxyl group, a C₁-C₂ alkoxy group or anoxygen bonded to a silicon atom of another monomer; each Z8 and Z9independently represent a hydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂alkyl group or an oxygen bonded to a silicon atom of another monomer;and each R¹ represents a nitrogen-containing C₄-C₁₀ alkyl group.

Embodiment 7

The organosilica material of embodiment 6, wherein each Z⁷ represents ahydroxyl group, methoxy, ethoxy, or an oxygen bonded to a silicon atomof another monomer; each Z⁸ and Z⁹ independently represent a hydroxylgroup, methoxy, ethoxy, methyl or an oxygen bonded to a silicon atom ofanother monomer; and each R¹ is selected from the group consisting of

Embodiment 8

The organosilica material of any one of the previous embodiments furthercomprising a monomer selected from the group consisting of:

-   -   (i) an independent unit of Formula [Z¹⁰OZ¹¹SiCH₂]₃ (IV), wherein        each Z¹⁰ represents a hydrogen atom, a C₁-C₄ alkyl group or a        bond to a silicon atom of another monomer and each Z¹¹        represents a hydroxyl group, a C₁-C₆ alkyl group or an oxygen        atom bonded to a silicon atom of another monomer;    -   (ii) an independent unit of Formula Z¹²OZ¹³Z¹⁴Z¹⁵Si (V), wherein        each Z² represents a hydrogen atom or a C₁-C₄ alkyl group or a        bond to a silicon atom of another monomer; and Z¹³, Z¹⁴ and Z¹⁵        are each independently selected from the group consisting of a        hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, and        an oxygen atom bonded to a silicon atom of another monomer;    -   (iii) an independent unit of Formula Z¹⁶Z¹⁷Z¹⁸Si—R²—SiZ¹⁶Z¹⁷Z¹⁸        (VI), wherein each Z¹⁶ independently represents a hydroxyl        group, a C₁-C₄ alkoxy group or an oxygen bonded to a silicon        atom of another comonomer; each Z¹⁷ and Z¹⁸ independently        represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl        group or an oxygen bonded to a silicon atom of another monomer;        and each R² is selected from the group consisting of a C₁-C₈        alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene        group an optionally substituted C₆-C₂₀ aralkyl and an optionally        substituted C₄-C₂₀ heterocycloalkyl group; and    -   (iv) a combination thereof.

Embodiment 9

The organosilica material of any one of the previous embodiments,wherein the organosilica has an average pore diameter between about 2.0nm and about 25.0 nm.

Embodiment 10

The organosilica material of any one of the previous embodiments,wherein the organosilica material has a total surface area of about 500m²/g to about 2000 m²/g.

Embodiment 11

The organosilica material of any one of the previous embodiments,wherein the organosilica material has a pore volume of about 3.0 cm³/gto about 3.0 cm³/g.

Embodiment 12

The organosilica material of any one of the previous embodiments,further comprising at least one catalytic metal incorporated within thepores of the material.

Embodiment 13

The organosilica material of embodiment 12, wherein the catalytic metalis selected from the group consisting of a Group 6 element, a Group 8element, a Group 9 element, a Group 10 element and a combinationthereof.

Embodiment 14

The organosilica material of any one of the previous embodiments madeusing essentially no structure directing agent or porogen.

Embodiment 15

A gas separation process comprising contacting a gas mixture containingat least one contaminant with the organosilica material of any one ofthe previous embodiments.

Embodiment 16

The process of embodiment 15, wherein the gas mixture comprises CH₄ andthe at least one contaminant is CO₂ and/or H₂S.

Embodiment 17

The process of embodiment 15 or 16, wherein the process comprises PSA,TSA, PPSA, PTSA, RCPSA, RCTSA, RC-PPSA or RC-PTSA.

Embodiment 18

A process for selectively separating a contaminant from a feed gasmixture, the process comprising:

-   -   a) contacting the feed gas mixture under sorption conditions        with the organosilica material of any one of embodiments 1-14;    -   b) adsorbing the contaminant into/onto the organosilica        material;    -   c) subjecting the organosilica material of any one of        embodiments 1-14 to desorption conditions by which at least a        portion of the sorbed contaminant is desorbed; and    -   d) retrieving a contaminant-rich product stream that has a        higher mol % of contaminant than the feed gas mixture.

Embodiment 19

The process of embodiment 18, wherein the feed gas mixture comprisesCH₄.

Embodiment 20

The process of embodiment 18 or 19, wherein the contaminant is CO₂and/or H₂S.

EXAMPLES General Methods Small Angle X-Ray Diffraction Analysis

X-ray powder diffraction (XRD) patterns were collected on a PANalyticalX'pert diffractometer equipped with an accessory for low anglemeasurements. XRD analyses were recorded using the Cu Ka (=1.5405980 Å)line in the 2θ range from 0.5 to 100 with a step size of 0.0167° and acounting time of 1.2 s.

Solid-State (SS) NMR Measurements

The ²⁹Si MAS NMR spectra were recorded on a Varian InfinityPlus-400spectrometer (operating at 9.4 T) and Varian InfinityPlus-500 (operatingat 11.74 T), corresponding to ²⁹Si Larmor frequencies of 79.4 MHz and99.2 MHz, respectively, with a 7.5 mm MAS probe heads using 5 kHzspinning, 4.0 μs 90° pulses, and at least 60 s recycle delay, withproton decoupling during data acquisition. The ²⁹Si chemical shifts arereferenced with respect to an external tetramethyl silane (δ_(si)=0.0ppm). The ¹³C CPMAS NMR spectra were recorded on a VarianInfinityPlus-500 spectrometer corresponding to ¹³C Larmor frequency of125 MHz, with 1.6 mm MAS probe head using 40 kHz spinning, ¹H-¹³Ccross-polarization (CP) contact time of at least 1 ms, a recycle delayof at least 1 s, with proton decoupling during data acquisition. The ¹³Cchemical shifts are referenced with respect to an external tetramethylsilane (δ_(C)=0.0 ppm). The ²⁷Al MAS NMR spectra were recorded on aVarian InfinityPlus-500 corresponding to ²⁷Al Larmor frequency of 130.1MHz using a 4 mm MAS probe head using 12 kHz spinning, with a π/12radian pulse length, with proton decoupling during data acquisition, anda recycle delay of 0.3 s. The chemical shifts are referenced withrespect to an external solution of Al(H₂O)₆ ³⁺ (δ_(Al)=0.0 ppm). All NMRspectra were recorded at room temperature using air for spinning.

Thermal Gravimetric Analysis (TGA)

Thermal stability results were recorded on Q5000 TGA. Ramp rate was 5°C./min, temperature range was from 25° C. to 800° C. All the sampleswere tested in both air and nitrogen.

CO₂ Adsorption

The work was done with a Quantchrom autosorb iQ2. All the samples werepre-treated at 120° C. in vacuum for 3 hours before collecting the CO₂isotherm at different temperatures.

Nitrogen Porosimetry

The nitrogen adsorption/desorption analyses was performed with differentinstruments, e.g. TriStar 3000, TriStar II 3020 and Autosorb-1. All thesamples were pre-treated at 120° C. in vacuum for 4 hours beforecollecting the N₂ isotherm. The analysis program calculated theexperimental data and report BET surface area (total surface area),microporous surface area (S), total pore volume, pore volume formicropores, average pore diameter (or radius), etc.

Example 1 Organosilica Material Syntheses Using Formula [R¹R²SiCH₂]₃(Ia) in Basic or Acidic Media

1A. Synthesis Using [(EtO)₂SiCH₂]₃ in Basic Aqueous Medium—withoutSurfactant.

A solution with 18.6 g of 30% NH₄OH and 23.76 g deionized water (DI)water was made. The pH of the solution was 12.55. To the solution, 3.0 gof 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane ([(EtO)₂SiCH₂]₃) wasadded, producing a mixture having the molar composition:

1.0[(EtO)₂SiCH₂]₃:21OH:270H₂O

and stirred for 1 day at room temperature (20-25° C.). The solution wastransferred to an autoclave and aged at 80° C.-90° C. for 1 day toproduce a gel. The gel was dried at 80° C. in a vacuum to remove most ofthe water and then fully dried at 110° C. for three hours. This producedSample 1A as a clear solid, which was converted to white powder aftergrinding. No surface directing agent or porogen were used in thispreparation.

The procedure was repeated with the following molar composition

4.0[(EtO)₂SiCH₂]₃:21OH:270H₂O

to produce Sample 1B.

XRD Analysis

XRD was performed on Sample 1A. The XRD pattern of Sample 1A is shown inFIG. 1.

TGA Analysis

TGA weight loss studies were performed on Sample 1A in nitrogen and air.FIGS. 2a and 2b display the TGA data for Sample 1A in nitrogen and air,respectively.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 1A, andthe results are provided in Table 1 below and FIGS. 3-6.

SS-NMR-Analysis

Sample 1A was characterized with ²⁹Si MAS NMR with the results as shownin FIG. 7 a.

1B. Comparative-Synthesis Using [(EtO)₂SiCH₂]₃ in Basic AqueousMedium—with Surfactant.

In this example, an organosilica material was prepared according toLandskron, K., et al., Science 302:266-269 (2003).

Cetyltrimethylammonium bromide (CTMABr, 0.9 mmol, 0.32 g, Aldrich) wasdissolved in a mixture of 2.16 g NH₄OH (35 wt %) and 3.96 g de-ionizedwater at 20° C. to form a solution.

[(EtO)₂SiCH₂]₃ (1.26 mmol, 0.5 g) was added to the solution, producing asolution having the molar composition:

1.0[(EtO)₂SiCH₂]₃:17OH:236H₂O:0.7CTMABr

which was stirred for 1 day at 20° C. and a white precipitate formed.Afterwards, the solution was aged for 1 day at 80° C. Then theprecipitate was filtered off and washed with water. The sample was thenstirred for 48 hours in a solution of 12 g HCl (36 wt %) and 80 g ofmethanol. The sample was then filtered off again and washed with MeOH,resulting in Comparative Sample 2.

XRD Analysis

XRD was performed Comparative Sample 2. A comparison of the XRD patternsfor Sample Al and Comparative Sample 2 is shown in FIG. 1. Compared tothe XRD pattern of Sample 1A, the XRD pattern of Comparative Sample 2exhibits a shoulder at about 3 degrees 2θ.

TGA Analysis

TGA weight loss studies were performed on Comparative Sample 2 innitrogen and air. FIGS. 8a and 8b display the TGA data for ComparativeSample 2 in nitrogen and air, respectively.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on ComparativeSample 2. The surface area, average pore diameter, and pore volumeobtained by the nitrogen adsorption/desorption analysis for Sample 1Aand Comparative Sample 2 are shown below in Table 1 and FIGS. 3 and 4.

TABLE 1 BET Pore Diameter Pore Volume Material (m²/g) (nm) (cc/g)Comparative Sample 2 1520 3.02 1.07 Sample 1A 1410 3.18 0.92

SS-NMR-Analysis

Comparative Sample 2 was characterized with ²⁹Si MAS NMR as shown inFIG. 7b . As shown below in Table 2, Sample 1A had a higher silanolcontent (i.e., 47%) compared to Comparative Sample 2 (i.e., 41%).

TABLE 2 D₁ D₂ T sites Si(OH)/Si Sample 1A (%) 96 4 47 45.6 50.4Comparative Sample 2(%) 89 11 41 34.7 54.3

1C. Synthesis Using [(EtO)₂SiCH₂]₃ in Acidic Aqueous Medium—withoutSurfactant.

A 14 g HCl solution with a pH of 2 was made by adding 0.778 mol waterand 0.14 mmol HCl. To the solution, 1.0 g (2.52 mmol) of [(EtO)₂SiCH₂]₃was added producing a solution having the molar composition:

18[(EtO)₂SiCH₂]₃:1HCl:5556H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 94° C. for 1 day toproduce a gel. The gel was dried in a vacuum at 120° C. overnight (16-24hours) to produce Sample 3. No surface directing agent or porogen wereused.

XRD Analysis

XRD was performed on Sample 3. A comparison of XRD patterns for Sample1A and Sample 3 is shown in FIG. 9.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 3. Thesurface area, microporous surface area, average pore diameter, and porevolume obtained by the nitrogen adsorption/desorption analysis forSample 3 are shown in FIGS. 5 and 6.

1D. Synthesis Using [(EtO)₂SiCH₂]₃ and [CH₃EtOSiCH₂]₃

A solution with 6.21 g of 30% NH₄OH and 7.92 g DI water was made. To thesolution, 0.6 g of [(EtO)₂SiCH₂]₃ and 0.306 g of1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane([CH₃EtOSiCH₂]₃) was added producing a solution having the molarcomposition:

1.5[(EtO)₂SiCH₂]₃:1.0[CH₃EtOSiCH₂]₃:53OH:682H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 90° C. for 1 day toproduce a gel. The gel was dried in a vacuum at 120° C. overnight (16-24hours) and Sample 4A was obtained. No structure directing agent orporogen were used.

Nitrogen Adsorption/Desorption Analysis

This above preparation method was repeated, except the relative ratio of[(EtO)₂SiCH₂]₃ (Reagent 1) to [CH₃EtOSiCH₂]₃ (Reagent 2) was varied.Nitrogen adsorption/desorption analysis was performed on each materialand the results for each material is given below in Table 3.

TABLE 3 Reagent BET V Pore Diameter Material 1:Reagent 2 (m²/g) (cc/g)(nm) Sample 1A 5:0 1410 0.915 3.18 Sample 4A 3:2 819 1.52 7.39 Sample 4B4:1 1100 1.14 4.17 Sample 4C 2:3 460 1.09 13.9 Sample 4D 0:5 1.817.73E−03 68.8

As Reagent 2 increased, the average pore diameter was observed toincrease, which without being bound by theory may be due to Reagent 2containing less reactive —OR groups compared to Reagent 1. The porosityof the material decreased as Reagent 2 was greater than 60% (mol ratio).

SS-NMR-Analysis

The materials in Table 3 were characterized with ²⁹Si MAS NMR, as shownin FIG. 10.

Example 2 Organosilica Material Syntheses Using Formula [R¹R²SiCH₂]₃(Ia) and Formula R³OR⁴R⁵R⁶Si (IIa) in Basic or Acidic Media

2A. Synthesis Using [(EtO)₂SiCH₂]₃ and Tetraethylorthosilicate (TEOS)((EtO)₄Si) in Basic Aqueous Medium

A solution with 6.21 g of 30% NH₄OH (53 mmol NH₄OH) and 7.92 g DI waterwas made. To the solution, 0.8 g (2 mmol) of [(EtO)₂SiCH₂]₃ and 0.625 g(3 mmol) of TEOS was added to produce a solution having the molarcomposition:

2.0[(EtO)₂SiCH₂]₃:3.0TEOS:53OH:682H₂O

which was stirred for three days at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 80° C.-90° C. for 2days to produce a gel. The gel was dried in a vacuum at 110° C.overnight (16-24 hours) and Sample 5 was obtained. No structuredirecting agent or porogen was used.

A solution with 6.21 g of 30% NH₄OH (53 mmol NH₄OH) and 7.92 g DI waterwas made. To the solution, 3.2 g (8 mmol) of [(EtO)₂SiCH₂]₃ and 2.5 g(12 mmol) of TEOS was added to produce a solution having the molarcomposition:

8.0[(EtO)₂SiCH₂]₃:12.0TEOS:53OH:682H₂O

which was stirred for three days at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 80° C.-90° C. for 2days to produce a gel. The gel was dried in a vacuum at 110° C.overnight (16-24 hours) and Sample 5A was obtained. No structuredirecting agent or porogen was used.

XRD Analysis

XRD was performed on Sample 5. The XRD pattern of Sample 5 is shown inFIG. 11.

TGA Analysis

TGA weight loss studies were performed on Sample 5 in nitrogen and air.FIG. 12 display the TGA data for Sample 5 in nitrogen and air.

SS-NMR-Analysis

Sample 5 was characterized with ²⁹Si MAS NMR and compared with Sample 1Aas shown in FIG. 13. As shown in FIG. 13, Sample 5 had a silanol contentof 44%.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 5 andSample 5A, and the results are provided below in Table 4 and FIGS. 5 and6.

TABLE 4 BET Pore Diameter Pore Volume Material (m²/g) (nm) (cc/g) Sample5 1430 3.42 1.21 Sample 5A 1027 4.84 1.202B. Synthesis Using [(EtO)₂SiCH₂]₃ and TEOS in Acidic Aqueous Medium

A 14 g HCl solution with a pH of 2 was made by adding 0.778 mol waterand 0.14 mmol HCl. To the solution, 0.8 g (2 mmol) of [(EtO)₂SiCH₂]₃ and0.625 g (3 mmol) TEOS was added to produce a solution having the molarcomposition:

2.0[(EtO)₂SiCH₂]₃:3.0TEOS:0.14H:778H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 94° C. for 1 day toproduce a gel. The gel was dried in a vacuum at 120° C. overnight (16-24hours) to produce Sample 6. No structure directing agent or porogen wereused.

XRD Analysis

XRD was performed on Sample 6. The XRD pattern of Sample 6 is shown inFIG. 11.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 6, andthe results are provided in FIGS. 5 and 6.

2C. Synthesis Using [CH₃EtOSiCH₂]₃ and TEOS

A solution with 6.21 g of 30% NH₄OH (53 mmol NH₄OH) and 7.92 g DI waterwas made. To the solution, 0.612 g (2 mmol) of1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane([CH₃EtOSiCH₂]₃) and 0.625 g (3 mmoles) of TEOS was added to produce asolution having the molar composition:

2.0[CH₃EtOSiCH₂]₃:3.0TEOS:53OH:682H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 90° C. for 1 day toproduce a gel. The gel was dried in a vacuum at 120° C. overnight (16-24hours) and Sample 7A was obtained. No structure directing agent orporogen were used.

Nitrogen Adsorption/Desorption Analysis

This above preparation method was repeated, except the relative ratio ofTEOS (Reagent 3) to [CH₃EtOSiCH₂]₃ (Reagent 2) was varied. Table 5 belowis a summary of the N₂ adsorption analysis for the materials obtainedwith varied reagent ratios.

TABLE 5 (Reagent BET Pore Volume Pore Diameter Material 3:Reagent 2)(m²/g) (cc/g) (nm) Sample 7A 3:2 471 1.9 18.6 Sample 7B 3:4 493 2.1623.1

SS-NMR-Analysis

The materials made by this method were characterized with by ²⁹Si MASNMR, as shown in FIG. 14.

2D. Synthesis Using [(EtO)₂SiCH₂]₃ and Methyltriethoxysilane (MTES)((EtO)₃CH₃Si)

A solution with 6.21 g of 30% NH₄OH (53 mmol NH₄OH) and 7.92 g DI waterwas made. To the solution, 0.4 g (1 mmol) of [(EtO)₂SiCH₂]₃ and 0.267 g(1.5 mmol) of MTES was added to produce a solution having the molarcomposition:

1.0[(EtO)₂SiCH₂]₃:1.5MTES:53OH:682H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 90° C. for 1 day toproduce a gel. The gel was dried in a vacuum at 120° C. overnight (16-24hours) and Sample 8A was obtained. No structure directing agent orporogen were used.

Nitrogen Adsorption/Desorption Analysis

This above preparation method was repeated, except the relative ratio of[(EtO)₂SiCH₂]₃ (Reagent 1) and of MTES (Reagent 2) was varied. Table 6below is a summary of the N₂ adsorption analysis for the materialsobtained with varied reagent ratios.

TABLE 6 Reagent BET Pore Volume Pore Diameter Material 1:Reagent 2(m²/g) (cc/g) (nm) Sample 1A 5:0 1410 0.915 3.18 Sample 8A 2:3 821 1.064.5 Sample 8B 4:1 1130 1.0 3.59 Sample 8C 3:2 1040 1.05 3.89

Example 3 Organosilica Material Syntheses Using Formula [R¹R²SiCH₂]₃(Ia) Formula R³OR⁴R⁵R⁶Si (IIa), and/or Formula Z¹⁹Z²⁰Z²¹Si—R—SiZ¹⁹Z²⁰Z²¹(IIa)

3A. Synthesis Using [(EtO)₂SiCH₂]₃ and CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃.

A solution with 6.21 g of 30% NH₄OH (53 mmol NH₄OH) and 7.9 g DI waterwas made. To the solution, 0.8 g (2 mmol) of [(EtO)₂SiCH₂]₃ and 0.88 g(3 mmol) 1,2-bis(methyldiethyoxysilyl)ethane(CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃) was added to produce a solution havingthe molar composition:

2.0[(EtO)₂SiCH₂]₃:3.0CH₃(EtO)₂Si—CH₂CH₂—Si(EtO)₂CH₃:53OH:682H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 80° C.-90° C. for 1day to produce a gel. The gel was dried in a vacuum at 110° C. overnight(16-24 hours) and Sample 9 was obtained. No structure directing agent orporogen were used.

XRD Analysis

XRD was performed on Sample 9. The XRD pattern of Sample 9 is shown inFIG. 15.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 9, andthe results are provided in Table 7.

3B. Synthesis Using [(EtO)₂SiCH₂]₃ and (EtO)₃Si—CH₂—Si(EtO)₃

A solution with 6.21 g of 30% NH₄OH (53 mmol NH₄OH) and 7.9 g DI waterwas made. To the solution, 0.8 g (2 mmol) of [(EtO)₂SiCH₂]₃ and 1.02 g(3 mmol) of bis(triethoxysilyl)methane ((EtO)₃Si—CH₂—Si(EtO)₃) was addedto produce a solution having the molar composition:

2.0[(EtO)₂SiCH₂]₃:3.0(EtO)₃Si—CH₂—Si(EtO)₃:53OH:682H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 80° C.-90° C. for 1day to produce a gel.

The gel was dried in a vacuum at 110° C. overnight (16-24 hours) andSample 10 was obtained. No structure directing agent or porogen wereused.

XRD Analysis

XRD was performed on Sample 10. The XRD pattern of Sample 10 is shown inFIG. 15.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 10, andthe results are provided in Table 7.

3C. Synthesis using TEOS and (EtO)₃Si—CH₂—Si(EtO)₃

A solution with 6.21 g of 30% NH₄OH (53 mmoles NH₄OH) and 7.92 g DIwater was made. To the solution, 1.7 g (5 mmol) ofbis(triethoxysilyl)methane ((EtO)₃Si—CH₂—Si(EtO)₃) and 0.416 g (2 mmol)of TEOS were added to produce a solution having the molar composition:

5.0(EtO)₃Si—CH₂—Si(EtO)₃:2.0TEOS:53OH:682H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 80° C.-90° C. for 1day to produce a gel. The gel was dried in a vacuum at 110° C. overnight(8-16 hours) and Sample 11A was obtained. No structure directing agentor porogen were used.

Two more preparations with different ratios of reagents were also made,one with a (EtO)₃Si—CH₂—Si(EtO)₃:TEOS molar ratio of 4:4 to obtainSample 11B and another with a (EtO)₃Si—CH₂—Si(EtO)₃:TEOS molar ratio of3:6 to obtain Sample 11C.

XRD Analysis

XRD was performed on Sample 11A. The XRD pattern of Sample 11A is shownin FIG. 15.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 11A, andthe results are provided in Table 7.

3D. Synthesis Using [(EtO)₂SiCH₂]₃ and (EtO)₃Si—CH═CH—Si(EtO)₃

A solution with 12.42 g of 30% NH₄OH (106 mmol NH₄OH) and 15.8 g DIwater was made. To the solution, 1.6 g (4 mmol) of [(EtO)₂SiCH₂]₃ and0.352 g (1 mmol) 1,2-bis(triethoxysilyl)ethylene((EtO)₃Si—CH═CH—Si(EtO)₃) was added to produce a solution having themolar composition:

4.0[(EtO)₂SiCH₂]₃:1.0(EtO)₃Si—CH═CH—Si(EtO)₃:106OH:1364H₂O

which was stirred for 1 day at room temperature (20-25° C.). Thesolution was transferred to an autoclave and aged at 80° C.-90° C. for 1day to produce a gel. The gel was dried in a vacuum at 110° C. overnight(8-16 hours) and Sample 12 was obtained. No structure directing agent orporogen were used.

XRD Analysis

XRD was performed on Sample 12. The XRD pattern of Sample 12 is shown inFIG. 15.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Sample 12, andthe results are provided in Table 7.

TABLE 7 BET S Pore Diameter Pore Volume Material (m2/g) (m2/g, micro)(nm) (cc/g) Sample 9 551 233 8.4 0.76 Sample 10 1270 512 3.35 0.96Sample 11A 870 0 3.83 0.84 Sample 12 1030 0 3.69 1.02

Example 4 Organosilica Material Syntheses Using Formula [R¹R²SiCH₂]₃(Ia) and Nitrogen-Containing Monomers

Synthesis:

-   1. Made a solution with 6.21 g 30% NH₄OH and 7.9 g DI water (53 mmol    NH₄OH; 682 mmol H₂O);-   2. Added 0.8 g (2 mmol) of [(EtO)₂SiCH₂]₃ (Reagent 1) to Reagent 2    into the above solution, kept stirring for 1 day at room    temperature;-   3. Transferred the solution to an autoclave, aging at 80-90° C. for    1 day;-   4. Dried the gel at 110° C. in vacuum overnight.

The above synthesis was performed with the following reagents in Table 8to obtain Samples 13, 14, 15 and 21.

The above synthesis was performed with the following reagents in Table 8to obtain Samples 16, 17, 18 and 19 except 1.6 g of Reagent 1, 12.4 g30% NH₄OH and 15.8 g DI water were used for the preparation.

The above synthesis was performed with the following reagents in Table 8to obtain Sample 20 except 3.2 g of Reagent 1, 24.8 g 30% NH₄OH and 31.6g of DI water were used for the preparation.

TABLE 8 Reagent 2 Reagent Amount 1:Reagent 2 Material Reagent 2 (g)Molar ratio Sample 13 N,N′-bis[(3-trimethoxy- 0.192 2:0.5silyl)propyl]ethylenediamine Sample 13A N,N′-bis[(3-trimethoxy- 2:3 silyl)propyl]ethylenediamine Sample 14 bis[(methyldiethoxy- 0.183 2:0.5silyl)propyl]amine Sample 15 bis[(methyldimethoxy- 0.162 2:0.5silyl)propyl]-N-methylamine Sample 16 (N,N-dimethylamino- 1.24 2:3 propyl)trimethoxysilane Sample 17 N-(2-aminoethyl)-3- 1.58 2:3 aminopropyltriethoxysilane Sample 18 4-methyl-1-(3-triethoxy- 1.83 2:3 silylpropyl)-piperazine Sample 19 4-(2-(triethoxysily)ethyl)pyridine0.271 2:0.5 Sample 20 1-(3-(triethoxysilyl)propyl)- 0.553 2:0.54,5-dihydro-1H-imidazole Sample 21 (3-aminopropyl)triethoxysilane 0.222:0.5

XRD Analysis

XRD was performed on Samples 13 and 21. The XRD patterns of Samples 13and 21 are shown in FIG. 16.

Nitrogen Adsorption/Desorption Analysis

Nitrogen adsorption/desorption analysis was performed on Samples 13, 14and 15, and the results are provided in Table 9 and FIGS. 17 and 18.

TABLE 9 BET Pore Diameter Pore Volume Material (m²/g) (nm) (cc/g) Sample13 1127 4.11 1.26 Sample 14 691 5 0.96 Sample 15 787 4.56 0.97

Example 5 CO₂ Isotherms

CO₂ adsorption isotherms were measured at 40° C. for Sample 13A and at30° C. for Sample 17, as shown in FIGS. 19 and 20, respectively.

What is claimed is:
 1. An organosilica material, which is a polymer of at least one independent monomer of Formula [Z¹OZ²OSiCH₂]₃ (I), wherein Z¹ and Z² each independently represent a hydrogen atom, a C₁-C₄ alkyl group or a bond to a silicon atom of another monomer and at least one other monomer selected from the group consisting of: (i) an independent unit of Formula Z³OZ⁴Z⁵Z⁶ (II), wherein each Z³ represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a silicon atom of another monomer; and Z⁴, Z⁵ and Z⁶ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, a nitrogen-containing C₁-C₁₀ alkyl group, a nitrogen-containing heteroaralkyl group, a nitrogen-containing optionally substituted heterocycloalkyl group, and an oxygen atom bonded to a silicon atom of another monomer; (ii) an independent unit of Formula Z⁷Z⁸Z⁹Si—R¹—SiZ⁷Z⁸Z⁹ (III), wherein each Z⁷ independently represents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen bonded to a silicon atom of another comonomer; each Z⁸ and Z⁹ independently represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygen bonded to a silicon atom of another monomer; and each R¹ represents a nitrogen-containing C₂-C₁₀ alkylene group; and (iii) a combination thereof.
 2. The organosilica material of claim 1, wherein Z¹ and Z² each independently represent a hydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom of another monomer.
 3. The organosilica material of claim 1, wherein Z¹ and Z² each independently represent a hydrogen atom, ethoxy or a bond to a silicon atom of another monomer.
 4. The organosilica material of claim 1, wherein at least one independent unit of Formula (II) is present, wherein each Z³ represents a hydrogen atom, a C₁-C₂ alkyl group or a bond to a silicon atom of another comonomer; and Z⁴, Z⁵ and Z⁶ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₂ alkyl group, C₁-C₂ alkoxy group, a nitrogen-containing C₄-C₁₀ alkyl group, a nitrogen-containing C₄-C₁₀ heteroaralkyl group, or a nitrogen-containing optionally substituted C₄-C₁₀ heterocycloalkyl group.
 5. The organosilica material of claim 4, wherein each Z³ represents a hydrogen atom, methyl, ethyl, or a bond to a silicon atom of another comonomer; and Z⁴, Z⁵ and Z⁶ are each independently selected from the group consisting of a hydroxyl group, methoxy, ethoxy

and an oxygen bonded to a silicon atom of another monomer.
 6. The organosilica material of claim 1, wherein at least one independent unit of Formula (III) is present, wherein each Z⁷ represents a hydroxyl group, a C₁-C₂ alkoxy group or an oxygen bonded to a silicon atom of another monomer; each Z⁸ and Z⁹ independently represent a hydroxyl group, a C₁-C₂ alkoxy group, a C₁-C₂ alkyl group or an oxygen bonded to a silicon atom of another monomer; and each R¹ represents a nitrogen-containing C₄-C₁₀ alkyl group.
 7. The organosilica material of claim 6, wherein each Z⁷ represents a hydroxyl group, methoxy, ethoxy, or an oxygen bonded to a silicon atom of another monomer; each Z⁸ and Z⁹ independently represent a hydroxyl group, methoxy, ethoxy, methyl or an oxygen bonded to a silicon atom of another monomer; and each R¹ is selected from the group consisting of


8. The organosilica material of claim 1 further comprising a monomer selected from the group consisting of: (i) an independent unit of Formula [Z¹⁰OZ¹¹SiCH₂]₃ (IV), wherein each Z¹⁰ represents a hydrogen atom, a C₁-C₄ alkyl group or a bond to a silicon atom of another monomer and each Z¹¹ represents a hydroxyl group, a C₁-C₆ alkyl group or an oxygen atom bonded to a silicon atom of another monomer; (ii) an independent unit of Formula Z¹²OZ¹³Z¹⁴Z¹⁵Si (V), wherein each Z¹² represents a hydrogen atom or a C₁-C₄ alkyl group or a bond to a silicon atom of another monomer; and Z¹³, Z¹⁴ and Z¹⁵ are each independently selected from the group consisting of a hydroxyl group, a C₁-C₄ alkyl group, a C₁-C₄ alkoxy group, and an oxygen atom bonded to a silicon atom of another monomer; (iii) an independent unit of Formula Z¹⁶Z¹⁷Z¹⁸Si—R²—SiZ¹⁶Z¹⁷Z¹⁸ (VI), wherein each Z¹⁶ independently represents a hydroxyl group, a C₁-C₄ alkoxy group or an oxygen bonded to a silicon atom of another comonomer; each Z¹⁷ and Z¹⁸ independently represent a hydroxyl group, a C₁-C₄ alkoxy group, a C₁-C₄ alkyl group or an oxygen bonded to a silicon atom of another monomer; and each R² is selected from the group consisting of a C₁-C₈ alkylene group, a C₂-C₈ alkenylene group, a C₂-C₈ alkynylene group an optionally substituted C₆-C₂₀ aralkyl and an optionally substituted C₄-C₂₀ heterocycloalkyl group; and (iv) a combination thereof.
 9. The organosilica material of claim 1, wherein the organosilica has an average pore diameter between about 2.0 nm and about 25.0 nm.
 10. The organosilica material of claim 1, wherein the organosilica material has a total surface area of about 500 m²/g to about 2000 m²/g.
 11. The organosilica material of claim 1, wherein the organosilica material has a pore volume of about 3.0 cm³/g to about 3.0 cm³/g.
 12. The organosilica material of claim 1, further comprising at least one catalytic metal incorporated within the pores of the material.
 13. The organosilica material of claim 12, wherein the catalytic metal is selected from the group consisting of a Group 6 element, a Group 8 element, a Group 9 element, a Group 10 element and a combination thereof.
 14. The organosilica material of claim 1 made using essentially no structure directing agent or porogen.
 15. A gas separation process comprising contacting a gas mixture containing at least one contaminant with the organosilica material of claim
 1. 16. The process of claim 15, wherein the gas mixture comprises CH₄ and the at least one contaminant is CO₂ and/or H₂S.
 17. The process of claim 15, wherein the process comprises PSA, TSA, PPSA, PTSA, RCPSA, RCTSA, RC-PPSA or RC-PTSA.
 18. A process for selectively separating a contaminant from a feed gas mixture, the process comprising: a) contacting the feed gas mixture under sorption conditions with the organosilica material of claim 1; b) adsorbing the contaminant into/onto the organosilica material; c) subjecting the organosilica material of claim 1 to desorption conditions by which at least a portion of the sorbed contaminant is desorbed; and d) retrieving a contaminant-rich product stream that has a higher mol % of contaminant than the feed gas mixture.
 19. The process of claim 18, wherein the feed gas mixture comprises CH₄.
 20. The process of claim 18, wherein the contaminant is CO₂ and/or H₂S. 